Curable composition

ABSTRACT

A curable composition including (A) a compound having two or more alkenyl groups and a perfluoro(poly)ether group in one molecule, wherein the perfluoro(poly)ether group is represented by formula: —(OC6F12)a—(OC5F10)b—(OC4F8)c—(OC3X106)d—(OC2F4)e—(OCF2)f—, a, b, c and d are each independently an integer of 0 to 30, e and f are each independently an integer of 1 to 200, the sum of a, b, c, d, e and f is at least 5, the occurrence order of the respective repeating units in parentheses with the subscript a, b, c, d, e or f is not limited in the formula, a ratio of e to f is 1.0 or more, and each X10 , at each occurrence, is independently a hydrogen atom, a fluorine atom or a chlorine atom, (B) an organosilicon compound which has two or more hydrogen atoms each bonding to a silicon atom, in one molecule, and (C) a catalyst.

TECHNICAL FIELD

The present invention relates to a curable composition.

BACKGROUND ART

A composition including a certain fluoropolyether-based compound hasexcellent water-repellency, oil-repellency, and the like. For example,Patent Literature 1 describes rubber where a cured film of a roomtemperature curing perfluoro(poly)ether composition is formed on thesurface of the rubber, and describes the following: there is providedrubber to which releaseability, solvent resistance, chemical resistance,weather resistance, water-repellency, oil-repellency, and the like areimparted. Examples of Patent literature 1 describe a composition using acompound having, as a perfluoro(poly)ether structure, (OCF₂CF(CF₃))_(m)OCF₂CF₂O (CF (CF₃) CF₂O)_(n), wherein m+n*90.

Examples of Patent Literature 2 describe an addition-curingfluoropolyether-based adhesive composition including a linear polyfluorocompound having the same perfluoro(poly)ether structure (OCF₂CF(CF₃))_(m)O(CF₂) ₂O(CF(CF₃)CF₂O)_(n), wherein m+n=90, as that in PatentLiterature 1 above. The linear polyfluoro compound of Patent Literature2 has not only the perfluoro(poly)ether structure, but also two or morealkenyl groups, in one molecule. Patent Literature 2 describes thefollowing: the composition enables a cured product having favorableadhesiveness to various metals or plastic base materials to be formed.

CITATION LIST Patent Literatures

Patent Literature 1: JP 2008-214566 A

Patent Literature 2: JP 2011-168768 A

SUMMARY OF INVENTION Technical Problem

In some field, for example, the field of a semiconductor manufacturingequipment, such a composition may be demanded to enable a cured productwhich is usable at a low temperature (for example, a temperature of 0°C. or less) to foe formed, depending on the application thereof. It,however, has been found according to studies by the present inventorthat a cured product of the composition described in Examples of PatentLiterature 1 or 2 may not keep the rubber properties when used at a lowtemperature and thus may be unsuitable for use at a low temperature. Asa decomposed material formed by heating may be a contamination source,the cured product thereof may be demanded to be hardly decomposed at ahigh temperature.

An object of the present invention is to provide a curable compositionwhich is suitable for forming a cured product suitable for use at a lowtemperature, for example, a cured product which has low elastic modulusratio at a low temperature (for example, the ratio of the elasticmodulus at −50° C. to the elastic modulus at 0° C.), and which issuitable for forming the cured product not easy to be decomposed at hightemperature.

Solution to Problem

A first aspect of the present invention provides a curable compositionincluding

(A) a compound which is a compound having two or more alkenyl groups anda perfluoro(poly)ether group in one molecule, wherein

the perfluoro(poly)ether group is a group represented by formula:

—(OC₆F₁₂)_(a)—(OC₅F₁₀)_(b)—(OC₄F₈)_(c)—(OC₃X¹⁰₆)_(d)—(OC₂F₄)_(e)—(OCF₂)_(f)—

wherein a, b, c and d are each independently an integer of 0 or more and30 or less, e and f are each independently an integer of 1 or more and200 or less, the sum of a, b, c, d, e and f is at least 5 or more, theoccurrence order of the respective repeating units in parentheses withthe subscript a, b, c, d, e or f is not limited in the formula, a ratioof e to f is 1.0 or more, and each X¹⁰, at each occurrence, isindependently a hydrogen atom, a fluorine atom or chlorine atom,

(B) an organosilicon compound which has two or more hydrogen atoms eachbonding to a silicon atom, in one molecule, and

(C) a catalyst.

Advantageous Effects of Invention

The present invention can provide a curable composition which issuitable for forming a cured product suitable for use at a lowtemperature, for example, a cured product with low elastic modulus ratioat a low temperature (for example, the ratio of the elastic modulus at−50° C. to the elastic modulus at 0° C.), and the cured product which ishardly decomposed at a high temperature.

DESCRIPTION OF EMBODIMENTS

Hereinafter, the curable composition of the present invention will bedescribed.

The divalent organic group, as used herein, means a divalent groupcontaining carbon. The divalent organic group is not limited, andexamples thereof include a divalent group where 1 to 9 hydrogen atomsare further removed from a hydrocarbon group. The divalent organic groupis not limited, and examples thereof include a divalent group where onehydrogen atom is further removed from a hydrocarbon group.

The curable composition of the present invention includes

(A) a compound which is a compound having two or more alkenyl groups anda perfluoro(poly)ether group in one molecule, wherein

the perfluoro(poly)ether group is a group represented by formula:

—(OC₆F₁₂)_(a)—(OC₅F₁₀)_(b)—(OC₄F₈)_(c)—(OC₃X¹⁰₆)_(d)—(OC₂F₄)_(e)—(OCF₂)_(f)—

wherein a, b, c and d are each independently an integer of 0 or more and30 or less, e and f are each independently an integer of 1 or more and200 or less, the sum of a, b, c, d, e and f is at least 5 or more, theoccurrence order of the respective repeating units in parentheses withthe subscript a, b, c, d, e or f is not limited in the formula, theratio of e to f is 1.0 or more, and each X¹⁰, at each occurrence, isindependently a hydrogen atom, a fluorine atom or a chlorine atom(hereinafter, sometimes referred to as “PFPE-containing compound (A)”),

(B) an organosilicon compound which has two or more hydrogen atoms eachbonding to a silicon atom, in one molecule (hereinafter, sometimesreferred to as “organosilicon compound (B)”), and

(C) a catalyst.

(PFPE-Containing Compound (A))

The PFPE-containing compound (A) has two or more alkenyl groups,preferably two alkenyl groups, in one molecule.

The alkenyl group is preferably a group having 2 to 8 carbon atoms, morepreferably a group having 2 to 6 carbon atoms. Examples of the alkenylgroup can include a vinyl group, an allyl group, a propenyl group, anisopropenyl group, a butenyl group and a hexenyl group, particularly avinyl group or an allyl group.

The alkenyl group is preferably present at each of both ends of amolecular backbone of the PFPE-containing compound (A). The molecularbackbone here represents a relatively longest binding chain in amolecule of the PFPE-containing compound (A).

The perfluoro(poly)ether group is a group represented by formula:

—(OC₆F₁₂)_(a)—(OC₅F₁₀)_(b)—(OC₄F₈)_(c)—(OC₃X¹⁰₆)_(d)—(OC₂F₄)_(e)—(OCF₂)_(f)—

In the formula, a, b, c and d are each independently an integer of 0 ormore and 30 or less, and e and f are each independently an integer of 1or more and 200 or less, preferably 5 or more and 200 or less, morepreferably 10 or more and 200 or less. Preferably, the sum of a, b, c,d, e and f is 5 or more, more preferably 10 or more, for example, 10 ormore and 200 or less. The occurrence order of the respective repeatingunits in parentheses with the subscript a, b, c. d, e or f is notlimited in the formula. The ratio of e to f (hereinafter, referred to as“e/f ratio”) is 1.0 or more. Each X¹⁰, at each occurrence, independentlyrepresents a hydrogen atom, a fluorine atom or a chlorine atom,preferably a hydrogen atom or a fluorine atom, more preferably afluorine atom. Hereinafter, the perfluoro(poly)ether group having such astructure is sometimes referred to as “PFPE¹”. The curable compositionof the present invention comprises such PFPE¹, and thus a cured productof the curable composition can have a low glass transition temperature(Tg).

Here, a and b are each independently preferably 0 or more and 30 orless, and, for example, may be 0.

In one embodiment, a, b, c and d are each independently preferably aninteger of 0 or more and 30 or less, more preferably an integer of 20 orless, particularly preferably an integer of 10 or less, furtherpreferably an integer of 5 or less, or, for example, may be 0.

In one embodiment, the sum of a, b, c and d is preferably 30 or less,more preferably 20 or less, further preferably 10 or less, particularlypreferably 5 or less.

In one embodiment, the sum of e and f is preferably 30 or more, morepreferably 40 or more, further preferably 50 or more.

Such repeating units may, for example, be linear or branched, and arepreferably linear. For example, —(OC₆F₁₂) — may be—(OCF₂CF₂CF₂CF₂CF₂CF₂)—, —(OCF(CF₃) CF₂CF₂CF₂CF₂)—, —(OCF₂CF(CF₃)CF₂CF₂CF₂)—, —(OCF₂CF₂CF(CF₃)CF₂CF₂)—, —(OCF₂CF₂CF₂CF(CF₃)CF₂)—,—(OCF₂CF₂CF₂CF₂CF(CF₃))—, or the like, and is preferably—(OCF₂CF₂CF₂CF₂CF₂CF₂)—. For example, —(OC₅F₁₀)— may be—(OCF₂CF₂CF₂CF₂CF₂)—, —(OCF(CF₃) CF₂CF₂CF₂)—, —(OCF₂CF(CF₃)CF₂CF₂)—,—(OCF₂CF₂CF(CF₃)CF₂)—, —(OCF₂CF₂CF₂CF (CF₃)) —, or the like, and ispreferably —(OCF₂CF₂CF₂CF₂CF₂)—, —(OC₄F₈)— may be any of—(OCF₂CF₂CF₂CF₂)—, —(OCF(CF₃)CF₂CF₂)—, —(OCF₂CF(CF₃)CF₂)—,—(OCF₂CF₂CF(CF₃))—, —(OC(CF₃)₂CF₂)—, —(OCF₂C(CF₃)₂)—,—(OCF(CF₃)CF(CF₃))—, —(OCF(C₂F₅)CF₂)— and —(OCF₂CF(C₂F₅))—, and ispreferably —(OCF₂CF₂CF₂CF₂)—. —(OC₃F₆)— (namely, in the formulae, X¹⁰represents a fluorine atom) may be any of —(OCF₂CF₂CF₂)—,—(OCF(CF₃)CF₂)— and —(OCF₂CF(CF₃))—, and is preferably —(OCF₂CF₂CF₂)—,—(OC₂F₄)— may be any of —(OCF₂CF₂)— and —(OCF(CF₃))—, and is preferably—(OCF₂CF₂)—.

In one embodiment, PFPE¹ has a linear repeating unit. In the presentembodiment, the molecular mobility of the PFPB-containing compound (A)is hardly decreased at a low temperature. A linear repeating unit iscontained, thereby enabling a physical property value (for example,elastic modulus at a low temperature) of the PFPE-containing compound(A) to be hardly decreased as compared with a value at room temperature.Herein, the “elastic modulus” indicates dynamic elastic modulus, morespecifically storage elastic modulus.

Preferably, PFPE¹ is —(OC₄F₈)_(c)—(OC₃F₆)_(d)—(OC₂F₄)_(e)—(OCF₂)_(f)—,wherein c and d are each independently an integer of 0 or more and 30 orless, e and f are each independently an integer of 1 or more and 200 orless, preferably 5 or more and 200 or less, more preferably 10 or moreand 200 or less, and the occurrence order of the respective repeatingunits in parentheses with the subscript c, d, e or f is not limited inthe formula. Preferably, PFPE¹ is—(OCF₂CF₂CF₂CF₂)_(c)—(OCF₂CF₂CF₂)_(d)—(OCF₂CF₂)_(e)—(OCF₂)_(f)—. In oneembodiment, PFPE¹ may be —(OCF₂F₄)_(e)—(OCF₂)_(f)—, wherein e and f areeach independently an integer of 1 or more and 200 or less, preferably 5or more and 200 or less, more preferably 10 or more and 200 or less, andthe occurrence order of the respective repeating units in parentheseswith the subscript e or f is not limited in the formulae.

More preferably, PFPE¹ is —(OC₂F₄)_(e)—(OCF₂)_(f)—, wherein e and f areeach independently an integer of 1 or more and 200 or less, preferably 5or more and 200 or less, more preferably 10 or more and 200 or less, andthe occurrence order of the respective repeating units in parentheseswith the subscript e or f is not limited in the formula.

In PFPE¹, the ratio of the sum of e and f to the sum of a, b, c, d, eand f is preferably 0.80 or more, more preferably 0.90 or more, furtherpreferably 0.98 or more, particularly preferably 0.99 or more.

In PFPE¹, the e/f ratio is preferably 1.0 or more, more preferably 1.1or more, further preferably 1.2 or more. The e/f ratio is preferably10.0 or less, more preferably 5.0 or less, further preferably 2.0 orless, particularly preferably 1.5 or less.

In PFPE¹, the e/f ratio is preferably 1.0 or more and 10.0 or less, morepreferably 1.0 or more and 5.0 or less, further preferably 1.0 or moreand 2.0 or less, particularly preferably 1.0 or more and 1.5 or less.

The curable composition of the present invention is hardly decomposed ata high temperature. The cured product being “hardly decomposed at a hightemperature” is herein means that the temperature of 1% decomposition ofthe cured product is relatively high temperature. That is, the curablecomposition of the present invention can contribute to formation of acured product usable in a wide temperature range. The “temperature of 1%decomposition” here means a temperature at which 1% by mass of a curedproduct relative to the entire cured product is decomposed. Thetemperature of 1% decomposition means a value obtained by measurementaccording to thermogravimetric/differential thermal analysis (TG/DTA),and is specifically measured in the range from 25° C. to 600° C. at atemperature-increasing rate of 10° C./min under an air atmosphere.Examples of the TG/DTA can include DTG-60 manufactured by ShimadzuCorporation.

A cured product of the curable composition of the present invention hasabove-mentioned PFPE¹, and thus can have an appropriate elastic moduluswhen used even at a low temperature (for example, the ratio of theelastic modulus at −50° C. to the elastic modulus at 0° C. can bedecreased). Accordingly, the curable composition of the presentinvention can contribute to formation of a cured product which can keeprubber properties even at a low temperature, and the cured product canbe suitable for use at a low temperature.

The number average molecular weight of the —PFPE¹— moiety can be in therange from 2,000 to 200,000, and is preferably in the range from 3,000to 100,000. The number average molecular weight is defined as a valueobtained by ¹⁹F-NMR measurement.

In one embodiment, the number average molecular weight of the —PFPE¹—moiety can be in the range from 2.000 to 10,000, and is preferably inthe range from 2.000 to 3,000. Such a number average molecular weight ofthe —PFPE¹— moiety enables the curable composition to be low inviscosity and favorable in handleability. The curable composition havingsuch a number average molecular weight of the —PFPE¹— moiety is alsoadvantageous from the viewpoint of suppression of viscosity in the casewhere the composition is used with a solvent to be thereby formed into asolution.

In one embodiment/the number average molecular weight of the —PFPE¹—moiety can be in the range from 10/000 to 100,000, and is preferably inthe range from 10/000 to 50,000. The compound can have such a numberaverage molecular weight of the —PFPE¹— moiety to thereby allow thecurable composition to be improved in physical properties such asstretching properties after curing.

The PFPE-containing compound (A) is preferably a compound represented bythe following formula (I).

CH₂═CH—R^(k1)—PFPE¹-R^(k1)—CH═CH₂   (I)

In formula (I), PFPE¹ has the same meaning as described above.

In formula (I), each R^(k1), at each occurrence, independentlyrepresents a single bond or a divalent organic group.

R^(k1) is understood to be a linker which links a perfluoro(poly)ethermoiety (namely, —PFPE¹— moiety) mainly providing water-repellency,surface lubricity, and the like, and an alkenyl group. Accordingly,R^(k1) may be a single bond or any organic group as long as thePFPE-containing compound (A) can be stably present. Herein, a leftportion and a right portion of R^(k1) are bonding to the grouprepresented by PFPE¹ and the —CH═CH₂ moiety of formula (I),respectively.

In another embodiment, R^(k1) can be X_(e). X_(e) represents a singlebond or a divalent organic group, preferably represents a single bond ora divalent organic group having at least one selected from the groupconsisting of —C₆H₄— (namely, -phenylene-, hereinafter, representing aphenylene group), —CO— (carbonyl group), —NR⁴— and —SO₂—. Each R⁴independently represents a hydrogen atom, a phenyl group, or a C₁₋₆alkyl group (preferably a methyl group), preferably represents ahydrogen atom or a methyl group. Such —C₆H₄—, —CO—, —NR⁴— or —SO₂— ispreferably contained in a molecular backbone of the PFPE-containingcompound (A). The molecular backbone here represents a relativelylongest binding chain in a molecule of the PPPE-containing compound (A).

X^(e) more preferably represents a single bond or a divalent organicgroup having at least one selected from the group consisting of —C₆H₄—,—CONR⁴—, —CONR⁴—C₆H₄—, —CO—, —CO—C₆H₄—, —SO₂NR₄—, —SO₂NR₆-13 C₆H₄—,—SO₂—, and —SO₂—C₆H₄—. Such —C₆H₄—, —CONR⁴—, —CONR⁴—C₆H₄—, —CO—,—co—C₆H₄—, —SO₂NR⁴—, —SO₂NR⁴—C₆H₄—, —SO₂—, or —SO₂—C₆H₄— is preferablycontained in a molecular backbone of the PFPE-containing compound (A).

Examples of ^(k1) are not limited, and include a divalent grouprepresented by the following formula:

—(R³¹)_(p′)—(X^(a))_(q′)—

wherein:

R³¹ represents a single bond, —(CH₂)_(s′)—, or an o-, m- or p-phenylenegroup, preferably represents —(CH₂)_(s′)—,

s′ is an integer of 1 to 20, preferably an integer of 1 to 6, morepreferably an integer of 1 to 3, still more preferably 1 or 2,

X^(a) represents, —(X^(b))_(1′)—,

each X^(b), at each occurrence, independently represents a groupselected from the group consisting of —O—, —S—, o-, m- or p-phenylenegroup, —C(O)O—, —Si(R³³)₂—, —(Si(R³³)₂O)_(m′)—Si (R³³)₂—, —CONR³⁴—,—O—CONR¹⁴—, —NR³⁴— and —(CH₂)_(s′)—,

each R³³, at each occurrence, independently represents a phenyl group, aC₁₋₆ alkyl group or a C₁₋₆ alkoxy group, preferably represents a phenylgroup or a C₁₋₆ alkyl group, more preferably represents a methyl group,

each R³⁴, at each occurrence, independently represents a hydrogen atom,a phenyl group, or a C₁₋₆ alkyl group (preferably a methyl group),

each m′, at each occurrence, is independently an integer of 1 to 100,preferably an integer of 1 to 20,

each n′, at each occurrence, is independently an integer of 1 to 20,preferably an integer of 1 to 6, more preferably an integer of 1 to 3,

1′ is an integer of 1 to 10, preferably an integer of 1 to 5, morepreferably an integer of 1 to 3,

p′ is 0 or 1, and

q′ is 0 or 1,

provided that at least one of p′ and q′ is 1, and the occurrence orderof the respective repeating units in parentheses with p′ or q′ is notlimited. Here, R³¹ and X^(a) (typically, any hydrogen atom in R³¹ andX^(a)) are each optionally substituted with one or more substituentsselected from a fluorine atom, a C₁₋₃ alkyl group and a C₁₋₃ fluoroalkylgroup.

In one embodiment, 1′ is 1.

Preferably, R^(k1) is —(R³¹)_(p′)—(X^(a))_(q′)—R³²—, R³² represents asingle bond, —(CH₂)_(t′), or an o-, m- or p-phenylene group, preferably—(CH₂)_(t′)—. Here, t′ is an integer of 1 to 20, preferably an integerof 2 to 6, more preferably an integer of 2 to 3. In one embodiment, t′is an integer of 1 to 6, more preferably an integer of 1 to 3, forexample, 1 or 2, more specifically 1. Here, R³² (typically, any hydrogenatom in R³²) is optionally substituted with one or more substituentsselected from a fluorine atom, a C₁₋₃ alkyl group and a C₁₋₃ fluoroalkylgroup.

Preferably, R^(k1) can be

-   a single bond,-   a C₁₋₂₀ alkylene group,-   —R³¹—X^(c)—R³²—, or-   —X^(d)—R³² —-   wherein R³¹ and R³² have the same meanings as described above.    Herein, such an alkylene group is a group having a —(CδH₂δ)—    structure, and is optionally substituted or unsubstituted and is    optionally linear or branched.

More preferably, R^(k1) is

-   a single bond,-   a C₁₋₂₀ alkylene group,-   —(CH₂)_(s′)—X^(c)—,-   —(CH₂)_(a′)—X^(c)—(CH₂)_(t′)—,-   —X^(d)—, or-   —X^(d)—(CH₂)_(t′)—-   wherein s′ and t′ have the same meanings as described above.

Further preferably, R^(k1) is

-   —X^(f)—,-   a —X^(f)—C₁₋₂₆ alkylene group,-   —X^(f)—(CH₂)_(s′)—X^(c)—,-   —X^(f)—(CH₂)_(s′)—X^(c)—(CH₂)_(t′)—-   —X^(f)—X_(d)—, or-   —X^(f)—X_(d)—(CH₂)_(t′)—-   wherein s′ and t′ have the same meanings as described above.

In the formulae, X^(f) is an alkylene group having 1 to 6 carbon atoms,preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, forexample, a methylene group. Any hydrogen atom in X^(f) is optionallysubstituted with one or more substituents selected from a fluorine atom,a C₁₋₃ alkyl group and a C₁₋₃ fluoroalkyl group, and is preferablysubstituted. X^(f) may be linear or branched, and is preferably linear.

In the formulae, X^(c) represents

-   —O—,-   —S—,-   —C(O)O—,-   —CONR³⁴—,-   —O—CONR³⁴—,-   —(Si(R³³)₂O)_(m′)—Si(R³³)₂—,-   —O—(CH₂)_(u′)—(Si(R³³)₂O)_(m′)—Si(R³³)₂—,-   —O—(CH₂)_(u′)—Si(R³³)₂—O—Si(R³³)₂—CH₂Ch₂—Si(R³³)₂—O—Si(R³³)₂—,-   —O—(CH₂)_(u′)—Si(OCH₃)₂OSi(OCH₃)₂—-   —CONR³⁴—(CH₂)_(u′)—(Si(R³³)₂O)_(m′)—Si(R³³)₂—,-   —CONR³⁴—(CH₂)_(u′)—N(R³⁴)—, or-   —CONR³⁴-(o-, m- or p-phenylene) —Si(R³³)₂—-   wherein R³³, R³⁴ and m′ have the same meanings as described above,    and

u′ is an integer of 1 to 20, preferably an integer of 2 to 6, morepreferably an integer of 2 to 3. X^(c) is preferably —O—.

In the formulae, X^(d) represents

-   —S—,-   —C(O)O—,-   —CONR³⁴—,-   —CONR³⁴—(CH₂)_(u′)—(Si(R³³)₂O)_(m′)—Si(R³³)₂—,-   —CONR³⁴—(CH₂)_(u′)—N(R³⁴)—, or-   —CONR³⁴-(o-, m- or p-phenylene) —Si(R³³)₂—-   wherein each symbol has the same meaning as described above.

Particularly preferably, R^(k1) is a group represented by

-   —X^(f) —,-   a —X^(f)—C₁₋₂₆ alkylene group,-   —X^(f)—(CH₂)_(s′)—X^(c)—, —X^(f)—(CH₂)_(s′)—X^(c)—(CH₂)_(t′)—-   —X^(f)—X^(d)—, or-   —X^(f)—X^(d)—(CH₂)_(t′—)-   wherein X^(f), s′ and t′ have the same meanings as described above;

X^(c) represents —O—, or —CONR³⁴—,

X^(d) represents —CONR³⁴—, and

each R³⁴, at each occurrence, independently represents a hydrogen atom,a phenyl group, or a C₁₋₄ alkyl group (preferably a methyl group).

In one embodiment, R^(k1) is a group represented by

-   —X^(f)—(CH₂)_(s′)—X^(c)—,-   —X^(f)—(CH₂)_(s′)—X^(c)—(CH₂)_(t′)—-   —X^(f)—X^(d)—, or-   —X^(f)—X^(d)—(CH₂)_(t′)—-   wherein X^(f), s′ and t′ have the same meanings as described above;

X^(c) represents —O— or —CONR³⁴—,

X^(d) represents —CONR³⁴—, and

each R³⁴, at each occurrence, independently represents a hydrogen atom,a phenyl group or a C₁₋₄ alkyl group (preferably a methyl group).

In one embodiment, R^(k1) can be,

-   a single bond,-   a C₁₋₂₀ alkylene group,-   —(CH₂)_(s′)—X^(c)—(CH₂)_(t′)—, or-   —X^(d)—(CH₂)_(t′)—-   wherein each symbol has the same meaning as described above.

Preferably, R^(k1) is

-   a single bond,-   C₁₋₂ alkylene group,-   —(CH₂)_(s′)—O—(CH₂)_(t′—,)-   —(CH₂)_(s′)—(Si(R³³)₂O)_(m′)—Si(R³³)₂—(CH₂)_(t′)—,-   —(CH₂)_(s′)—O—(CH₂)_(u′)—(Si(R³³)₂O)_(m′)—Si(R³³)₂—(CH₂)_(t′)—, or-   —(CH₂)_(s′)—O—(CH₂)_(t′)—Si(R³³)₂—(CH₂)_(u′)—Si(R³³)₂—(C_(v)H_(2v))—-   wherein R³³, m′, s′, t′ and u′ have the same meanings as described    above, and v is an integer of 1 to 20, preferably an integer of 2 to    6, more preferably an integer of 2 to 3.

In the formulae, —(C_(v)H_(2v))— is optionally linear or branched, andcan be, for example, —CH₂—, —CH₂CH₂—, —CH₂CH₂Ch₂—, —CH(CH₃)— or—CH(CH₃)CH₂—,

The R^(k1) group is optionally substituted with one or more substituentsselected from a fluorine atom, a C₁₋₃ alkyl group and a C₁₋₃ fluoroalkylgroup (preferably C₁₋₃perfluoroalkyl group).

In one embodiment, the R^(k1) group can be other than a —O—C₁₋₆ alkylenegroup. in another embodiment., examples of the R^(k1) group include thefollowing groups:

wherein each R⁴¹ independently represents a hydrogen atom, a phenylgroup, an alkyl group having 1 to 6 carbon atoms, or a C₁₋₆ alkoxygroup, preferably a methyl group:

D is a group selected from

-   —CH₂O(CH₂)₂—,-   —CH₂O(CH₂)₃—,-   —CF₂O(CH₂)₃—,-   —(CH₂)₂—,-   —(CH₂)₃—,-   —(CH₂)₄—,-   —CONH—(CH₂)₃—,-   —CON(CH₃)—(CH₂)₃—,-   CON(Ph)—(CH₂)₃—, wherein Ph means phenyl, and

wherein each R⁴² independently represents a hydrogen atom, a C₁₋₆ alkylgroup or a C₁₋₆ alkoxy group, preferably a methyl group or a methoxygroup, more preferably a methyl group;

E is —(CH₂)_(ne)— (ne is an integer of 2 to 6),

D is bonding to PFPE¹ of a molecular backbone, and E is bonding to agroup opposite to PFPE¹.

Specific examples of R^(k1) include:

-   a single bond,-   —CH₂OCH₂—,-   —CH₂O(CH₂)₂—,-   —CH₂O(CH₂)₃—,-   —CH₂O(CH₂)₄—,-   —CF₂—CH₂—O—CH₂—,-   —CF₂—CH₂—O—(CH₂)₂—,-   —CF₂—CH₂—O—(CH₂)₃—,-   —CF₂—CH₂—O—(CH₂)₆—,-   —CH₂O(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂—,-   —CH₂O(CH₂)₃Si(CH₃)₂OSi(CH₃)₂OSi(CH₃)₂(CH₂)₂—,-   —CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂—,-   —CH₂O(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₃Si(CH₃)₂(CH₂)₂—,-   —CH₂O(CH₃)₃Si(CH₃)₂O(Si(CH₃)₂O)₁₀Si(CH₃)₂(CH₂)₂—,-   —CH₂O(CH₃)₃Si(CH₃)₂O(Si(CH₃)₂O)₂₀Si(CH₃)₂(CH₂)₂—,-   —CH₂OCF₂CHFOCF₂—,-   —CH₂OCF₂CHFOCF₂CF₂—,-   —CH₂OCF₂CHFOCF₂CF₂CF₃—,-   —CH₂OCH₂CF₂CF₂OCF₂—,-   —CH₂OCH₂CF₂CF₂OCF₂CF₂—,-   —CH₂OCH₂CF₂CF₂OCF₂CF₂CF₂—,-   —CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂—,-   —CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂—,-   —CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂CF₂—,-   —CH₂OCH₂CHFCF₂OCF₂—,-   —CH₂OCH₂CHFCF₂OCF₂CF₂—,-   —CH₂OCH₂CHFCF₂OCF₂CF₂CF₂—,-   —CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂—,-   —CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₃—,-   —CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂CF₂—,-   —CH₂OCF₂CHFOCF₂CF₂CF₂—C(O)NH—CH₂—,-   —-   CH₂OCH₂(CH₂)₇CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂Si(OCH₃)₂OSi(OCH₃)₂(C    H₂)₂—,-   —CH₂OCH₂CH₂CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₃—,-   —CH₂OCH₂CH₂CH₂Si(OCH₂CH₃)₂OSi(OCH₂CH₃)₂(CH₂)₃—,-   —CH₂OCH₂CH₂CH₂Si(OCH₃)₂OSi(OCH₃)₂(CH₂)₂—,-   —CH₂OCH₂CH₂CH₂Si(OCH₂CH₃)₂OSi(OCH₂CH₃)₂(CH₂)₂—,-   —(CH₂)₂—Si(CH₃)₂—(CH₂)₂—,-   —CH₂—,-   —(CH₂)₂—,-   —(CH₂)₃—,-   —(CH₂)₄—,-   —(CH₂)₅—,-   —(CH₂)₆—,-   —CF₂—,-   —(CF₂)₂—,-   —CF₂—CH₂—,-   —CF₂—(CH₂)₂—,-   —CF₂—(CH₂)₃—,-   —CF₂—(CH₂)₄—,-   —CF₂—(CH₂)₅—,-   —CF₂—(CH₂)₆—,-   —CO—,-   —CONH—,-   —CONH—CH₂—,-   —CONH—(CH₂)₂—,-   —CONH—(CH₂)₂—,-   —CONH—(CH₂)₆—,-   —CF₂CONH—,-   —CF₂CONHCH₂—,-   —CF₂CONH(CH₂)₂—,-   —CF₂CONH(CH₂)₃—,-   —CF₂CONH(CH₂)₆—,-   —CON(CH₃)—(CH₂)₃—,-   —CON(Ph)—(CH₂)₃—, wherein Ph means phenyl,-   —CON(CH₃)—(CH₂)₆—,-   —CON(Ph)—(CH₂)₆—, wherein Ph means phenyl,-   —CF₂—CON(CH₃)—(CH₂)₃—,-   —CF₂—CON(Ph)—(CH₂)₃—, wherein Ph means phenyl,-   —CF₂—CON(CH₃)—(CH₂)₆—,-   —CF₂—CON(Ph)—(CH₂)₆—, wherein Ph means phenyl,-   —CONH—(CH₂)₂NH(CH₂)₃—,-   —CONH—(CH₂)₆NH(CH₂)₃—,-   —CH₂O—CONH—(CH₂)₃—,-   —CH₂O—CONH—(CH₂)₆—,-   —S—(CH₂)₃—,-   —(CH₂)₂S(CH₂)₃—,-   —CONH—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂(CH₂)₂—,-   —CONH—(CH₂)₃Si(CH₃)₂OSi(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂—,-   —CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂Si(CH₃)₂(CH₂)₂—,-   —CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₃Si(CH₃)₂(CH₂)₂—,-   —CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₁₀Si(CH₃)₂(CH₂)₂—,-   —CONH—(CH₂)₃Si(CH₃)₂O(Si(CH₃)₂O)₂₀Si(CH₃)₂(CH₂)₂—,-   —C(O)O—(CH₂)₃—,-   —C(O))—(CH₂)₆—,-   —CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(CH₂)₂—,-   —CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—CH(CH₃)—,-   —CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—(Ch₃)₃—,-   —CH₂—O—(CH₂)₃—Si(CH₃)₂—(CH₂)₂—Si(CH₃)₂—CH(CH₃)—CH₂—,-   —OCH₂—,-   —O(CH₂)₃—,-   —OCFHCF₂—,

In particular, R^(k1) is preferably

-   —CH₂OCH₂—,-   —CH₂O(CH₂)₂—,-   —CH₂O(CH₂)₃—,-   —CH₂O(CH₂)₆—,-   —CF₂—CH₂—O—CH₂—,-   —CF₂—CH₂—O—(CH₂)₂—,-   —CF₂—CH₂—O—(CH₂)₃—,-   —CF₂—CH₂—O—(Ch₂)₆—,-   —CH₂OCF₂CHFOCF₂—,-   —CH₂OCF₂CHFOCF₂CF₂—,-   —CH₂OCF₂CHFOCF₂CF₂CF₂—,-   —CH₂OCH₂CF₂CF₂OCF₂—,-   —CH₂OCH₂CF₂CF₂OCF₂CF₂—,-   —CH₂OCH₂CF₂CF₂OCF₂CF₂CF₃—,-   —CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂—,-   —CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂—,-   —CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂CF₂—,-   —CH₂OCH₂CHFCF₂OCF₂—,-   —CH₂OCH₂CHFCF₂OCF₂CF₂—,-   —CH₂OCH₂CHFCF₂OCF₂CF₂CF₂—,-   —CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂—,-   —CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂—,-   —CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂CF₂—,-   —CH₂OCF₂CHFOCF₂CF₂CF₂—C(O)NH—CH₂—,-   —CH₂—,-   —(CH₂)₂—,-   —(CH₂)₃—,-   —(CH₂)₄—,-   —(CH₂)₅—,-   —(CH₂)₆—,-   —CF₂—,-   —(CF₂)₂—,-   —CF₂—CH₂—,-   —CF₂—(CH₂)₂—,-   —CF₂—(CH₂)₃—,-   —CF₂—(CH₂)₄—,-   —CF₂—(CH₂)₅—,-   —CF₂—(CH₂)₆—,-   —CONH—,-   —CONH—CH₂—,-   —CONH—(CH₂)₂—,-   —CONH—(CH₂)₃—,-   —CONH—(CH₂)₅—,-   —CF₂CONH—,-   —CF₂CONHCH₂—,-   —CF₂CONH(CH₂)₂—,-   —CF₂CONH(CH₂)₃—,-   —CF₂CONH(CH₂)₆—,-   —CON(CH₃)—(CH₂)₃—,-   —CON(Ph)—(CH₂)₃—, wherein Ph means phenyl ,-   —CON(CH₃)—(CH₂)₆—,-   —CON(Ph)—(CH₂)₆—, where Ph means phenyl-   —CF₂—CON(CH₃)—(CH₂)₃—,-   —CF₂—CON(Ph)—(CH₂)₃—, wherein Ph means phenyl,-   —CF₂—CON(CH₃)—(CH₂)₆—,-   —CF₂—CON(Ph)—(CH₂)₆—, wherein Ph means phenyl,-   —CONH—(CH₂)₂NH(CH₂)₃—,-   —CONH—(CH₂)₆NH(CH₂)₃—,-   —CH₂O—CONH—(CH₂)₃—,-   —CH₂O—CONH—(CH₂)₆—,-   —OCH₂—,-   —O(CH₂)₃—,

In the above st further referable preferably include

-   —CH₂OCH₂—,-   —CH₂O(CH₂)₂—,-   —CH₂O(CH₂)₃—,-   —CH₂O(CH₂)₆—,-   —CF₂—CH₂—O—CH₂—,-   —CF₂—CH₂—O—(CH₂)₂—,-   —CF₂—CH₂—O—(CH₂)₃—,-   —CF₂—CH₂—O—(CH₂)₆—,-   —CH₂OCF₂CHFOCF₂—,-   —CH₂OCF₂CHFOCF₂CF₂—,-   —CH₂OCF₂CHFOCF₂CF₂CF₂—,-   —CH₂OCH₂CF₂CF₂OCF₂—,-   —CH₂OCH₂CF₂CF₂OCF₂CF₂—,-   —CH₂OCH₂CF₂CF₂OCF₂CF₂CF₂—,-   —CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂—,-   —CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂—,-   —CH₂OCH₂CF₂CF₂OCF(CF₃)CF₂OCF₂CF₂CF₂—,-   —CH₂OCH₂CHFCF₂OCF₂—,-   —CH₂OCH₂CHFCF₂OCF₂CF₂—,-   —CH₂OCH₂CHFCF₂OCF₂CF₂CF₂—,-   —CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂—,-   —CH₂OCH₂CHFCF₂OCF(CF₃)CF₂OCF₂CF₂—,-   —CH₂OCF₂CHFOCF₂CF₂CF₂—C(O)NH—CH₂—,-   —CONH—,-   —CONH—CH₂—,-   —CONH—(CH₂)₂—,-   —CONH—(CH₂)₃—,-   —CONH—(CH₂)₆—,-   —CF₂CONH—,-   —CF₂CONHCH₂—,-   —CF₂CONH(CH₂)₂—,-   —CF₂CONH(CH₂)₃—,-   —CF₂CONH(CH₂)₆—,-   —CON(CH₃)—(CH₂)₃—,-   —CON(Ph)—(CH₂)₃—, wherein Ph means phenyl,-   —CON(CH₃)—(CH₂)₆—,-   —CON(Ph)—(CH₂)₆—, wherein Ph means phenyl,-   —CF₂—CON(CH₃)—(CH₂)₃—,-   —CF₂—CON(Ph)—(CH₂)₃—, wherein Ph means phenyl,-   —CF₂—CON(CH₃)—(CH₂)₆—,-   —CF₂—CON(Ph)—(CH₂)₆—, wherein Ph means phenyl,-   —CONH—(CH₂)₂NH(CH₂)₃—,-   —CONH—(CH₂)₆NH(CH₂)₃—,

In one embodiment, R^(k1) represents X^(e)′, X^(e)′ is a single bond, analkylene group having 1 to 6 carbon atoms —R⁵¹—C₆H₄—R⁵²—,—R⁵¹—CONF⁴—R⁵²—, —R⁵¹—CONR⁴—C₆H₄—R⁵²—, —R⁵¹—CO—R⁵²—, —R⁵¹—CO—C₆H₄—R⁵²—,—R⁵¹—SO₂NR⁴—R⁵²—, —R⁵¹—SO₂NR⁴—C₆H₄—R⁵²—, —R⁵¹—SO₂—R⁵²—, or —R⁵¹—SO₂—C₆H₄—R⁵²—. R⁵¹ and R⁵² each independently represent a single bondor an alkylene group having 1 to 6 carbon atoms, preferably a singlebond or an alkylene group having 1 to 3 carbon atoms. R⁴ has the samemeaning as described above. The alkylene group Is substituted orunsubstituted, preferably unsubstituted. Examples of the substituent ofthe alkylene group can include a halogen atom, preferably a fluorineatom. The alkylene group is linear or branched, preferably linear.

In a preferable embodiment, X^(e)′ can be a single bond.

-   —X^(f)—,-   an alkylene group having 1 to 6 carbon atoms, preferably 1 to 3    carbon atoms-   a —X^(f)—C₁₋₆ alkylene group, preferably a —X^(f)—C₁₋₃ alkylene    group, more preferably-   a —X^(f)—C₁₋₂ alkylene group,-   —C₆H₄—R⁵²′—,-   —CONR⁴′—R⁵²′—,-   —CONR⁴′—C₆H₄—R⁵²′—,-   —X^(f)—CONR⁴′—R⁵²′—,-   —X^(f)—CONR⁴′—C₆H₄—R⁵²′—,-   —CO—R⁵²′—,-   —CO—C₆H₄—R⁵²′—,-   —SO₂NR⁴′—R⁵²′—,-   —SO₂NR⁴′—C₆H₄—R⁵²′—,-   —SO₂—R⁵²′—,-   —SO₂—C₆H₄—R⁵²′—,-   ——R⁵¹′—C₆H₄—,-   —R⁵¹′—CONR⁴′—,-   —R⁵¹′—CONR⁴′—C₆H₄—,-   —R⁵¹′—CO—,-   —R⁵¹′—CO—C₆H₄—,-   —R⁵¹′—SO₂NR⁴′—,-   —R⁵¹′—SO₂NR⁴′—C₆H₄—,-   —R⁵¹′—SO₂—,-   —R⁵¹′—SO₂—C₆H₄—,-   —C₆H₄—,-   —CONR⁴′—,-   —CONR⁴′—C₆H₄—,-   —X^(f)—CONR⁴′—,-   —X_(f)—CONR⁴′—C₆H₄—,-   —CO—,-   —CO—C₆H₄—,-   —SO₂NR⁴′—,-   —SO₂NR⁴′—C₆H₄—,-   —SO₂—, or-   —SO₂—C₆H₄—-   wherein R⁵¹′ and R⁵²′ each independently a linear alkylene group    having 1 to 6carbon atoms, preferably 1 to 3 carbon atoms, the    alkylene group is substituted or unsubstituted, as described above,    and examples of the substituent of the alkylene group can include a    halogen atom, preferably a fluorine atom, and

R⁴′ is a hydrogen atom or a methyl group.

In particular, X^(e)′ can be preferably —X^(f)—,

-   an alkylene group having 1 to 6 carbon atoms, preferably 1 to 3    carbon atoms, or-   a —X^(f)—C₁₋₂ alkylene group,-   —CONR⁴′—R⁵²′—,-   —CONR⁴′—C₆H₄—R⁵²′—,-   —X^(f)—CONR⁴′—R⁵²′—,-   —X^(f)—CONR⁴′—C₆H₄—R⁵²′—,-   —R⁵¹′—CONR⁴′—,-   —R⁵¹′—CONR⁴′—C₆H₄—,-   —CONR⁴′—,-   —CONR⁴′—C₆H₄—,-   —X^(f)—CONR⁴′—,-   —X^(f)—CONR⁴′—C₆H₄—,-   —R⁵¹′—CONR⁴′—, or-   —R⁵¹′—CONR⁴′—C₆H₄—. In the formulae, X^(f), R⁴′, R⁵¹′ and R⁵²′ each    have the same meanings as described above.

In particular, X^(e)′ can be more preferably

-   —CONR⁴′—R⁵²′—,-   —CONR⁴′—C₆H₄—R⁵²′—,-   —X^(f)—CONR⁴′—R⁵²′—,-   —X^(f)—CONR⁴′—C₆H₄—R⁵²′—,-   —R⁵¹′—CONR⁴′—,-   —R⁵¹′—CONR⁴′—C₆H₄—,-   —CONR⁴′—,-   —CONR⁴′—C₆H₄—,-   —X^(f)—CONR⁴′—, or-   —X^(f)—CONR⁴′—C₆H₄—.

Specific examples of X^(e)′ in the present embodiment include

-   a single bond,-   a perfluoroalkylene group having 1 to 6 carbon atoms (for example,    —CF₂— and —(CF₂)₂—),-   an alkylene group having 1 to 6 carbon atoms,-   a —CF₂—C₁₋₆ alkylene group,-   —CONH—,-   —CONH—CH₂—,-   —CONH—(CH₂)₂—,-   —CONH—(CH₂)₃—,-   —CF₂—CONH—,-   —CF₂CONHCH₂—,-   —CF₂CONH(CH₂)₂—,-   —CF₂CONH(CH₂)₃—,-   —CON(CH₃)—,-   —CON(CH₃)—CH₂—,-   —CON(CH₃)—(CH₂)₂—,-   —CON(CH₃)—(CH₂)₃—,-   —CF₂—CON(CH₃)—,-   —CF₂—CON(CH₂)CH₂—,-   —CF₂—CON(CH₃)—(CH₂)₂—,-   —CF₂—CON(CH₃)—(CH₂)₃—,-   —CH₂—CONH—,-   —CH₂—CONH—CH₂—,-   —CH₂—CONH—(CH₂)₂—,-   —CH₂—CONH—(CH₂)₃—,-   —CF₂—CH₂—CONH—,-   —CF₂—CH₂—CONH—CH₂—,-   —CF₂—CH₂—CONH—(CH₂)₂—,-   —CF₂—CH₂—CONH—(CH₂)₃—,-   —CONH—C₆H₄—,-   —CON(CH₃)—C₆H₄—,-   —CH₂—CON(CH₃)—CH₂—,-   —CH₂—CON(CH₃)—(CH₂)₂—,-   —CH₂—CON(CH₃)—(CH₂)₃—,-   —CON(CH₃)—C₆H₄—,-   —CF₂—CONH—C₆H₄—,-   —CF₂—CON(CH₃)—C₆H₄—,-   —CF₂—CH₂—CON(CH₃)—CH₂—,-   —CF₂—CH₂—CON(CH₃)—CH₃—,-   —CF₂—CON(CH₃)—C₆H₆—,-   —CO—,-   —CO—C₆H₄—,-   —C₆H₄—,-   —SO₂NH—,-   —SO₂NH—CH₂—,-   —SO₂NH—(CH₂)₂—,-   —SO₂NH —(CH₂)₃—,-   —SO₂NH—C₆H₄—,-   —SO₂N(CH₃)—,-   —SO₂N(CH₃)—CH₂—,-   —SO₂N(CH₃)—(CH₂)₂—,-   —SO₂N(CH₃)—(CH₂)₃—,-   —SO₂N(CH₃)—C₆H₄—,-   —SO₂—,-   —SO₂—CH₂—,-   —SO₂—(CH₂)₂—,-   —SO₂—(CH₂)₃—, or-   —SO₂—C₆H₄—,

In the above list, examples of preferable X^(e)′ include aperfluoroalkylene group having 1 to 6 carbon atoms (for example, —CF₂—and —(CF₂)₂—),

-   an alkylene group having 1 to 6 carbon atoms, a —CF₂—C₂₋₆ alkylene    group,-   —CONH—,-   —CONH—CH₂—,-   —CONH—(CH₂)₂—,-   —CONH—(CH₂)₃—,-   —CF₂CONH—,-   —CF₂CONHCH₂—,-   —CF₂CONH(CH₂)₂—,-   —CF₂CONH(CH₂)₃—,-   —CON(CH₃)—,-   —CON(CH₃)—CH₂—,-   —CON(CH₃)—(CH₂)₂—,-   —CON(CH₃)—(CH₂)₃—,-   —CF₂—CON(CH₃)—,-   —CF₂—CON(CH₃)CH₂—,-   —CF₂—CON(CH₃)—(CH₂)₂—,-   —CF₂—CON(CH₃)—(CH₂)₃—,-   —CH₂—CONH—,-   —CH₂—CONH—CH₂—,-   —CH₂—CONH—(CH₂)₂—,-   —CH₂—CONH—(CH₂)₃—,-   —CF₂—CH₂—CONH—,-   —CF₂—CH₂—CONH—CH₂—,-   —CF₂—CH₂—CONH—(CH₂)₂—,-   —CF₂—CH₂—CONH—(CH₂)₃—,-   —CONH—C₆H₄—,-   —CON (CH₃)—C₆H₄—,-   —CH₂—CON(CH₃)—CH₂—,-   —CH₂—CON(CH₃)—(CH₂)₂—,-   —CH₂—CON(CH₃)—(CH₂)₃—,-   —CON(CH₃)—C₆H₄—-   —CF₂—CONH—C₆H₄—,-   —CF₂—CON(CH₃)—C₆H₄—,-   —CF₂—CH₂—CON(CH₃)—CH₂—,-   —CF₂—CH₂—CON(CH₃)—(CH₂)₂—,-   —CF₂—CH₂—CON(CH₃)—(CH₂)₃—, and-   —CF₂—CON(CH₃)—C₆H₄—.

In the above list, examples of more preferable X^(e)′ include

-   —CONH—,-   —CONH—CH₂—,-   —CONH—(CH₂)₂—,-   —CONH—(CH₂)₃—,-   —CF₂CONH—,-   —CF₂CONHCH₂—,-   —CF₂CONH(CH₂)₂—,-   —CF₂CONH(CH₂)₃—,-   —CON(CH₃)—,-   —CON(CH₃)—CH₂—,-   —CON(CH₃)—(CH₂)₂—,-   —CON(CH₃)—(CH₂)₃—,-   —CF₂—CON(CH₃)—,-   —CF₂—CON(CH₃)CH₂—,-   —CF₂—CON(CH₃)—(CH₂)₂—,-   —CF₂—CON(CH₃)—(CH₂)₃—,-   —CH₂—CONH—,-   —CH₂—CONH—CH₂—,-   —CH₂—CONH—(CH₂)₂—,-   —CH₂—CONH—(CH₂)₃—,-   —CF₂—CH₂—CONH—,-   —CF₂—CH₂—CONH—,-   —CF₂—CH₂—CONH—CH₂—,-   —CF₂—CH₂—CONH—(CH₂)₂—,-   —CF₂—CH₂—CONH—(CH₂)₃—,-   —CONH—C₆H₄—,-   —CON(CH₃)—C₆H₄—,-   —CH₂—CON(CH₃)—CH₂—,-   —CH₂—CON(CH₃)—(CH₂)₂—,-   —CH₂—CON(CH₃)—(CH₂)₃—,-   —CON(CH₃)—C₆H₄—-   —CF₂—CONH—C₆H₄—,-   —CF₂—CON(CH₂)—C₆H₄—,-   —CF₂—CH₂—CON(CH₃)—CH₂—,-   —CF₂—CH₂—CON(CH₃)—(CH₂)₂—,-   —CF₂—CH₂—CON(CH₃)—(CH₂)₃—, or-   —CF₂—CON(CH₃)—C₆H₄—,

In one embodiment, X^(e)′ is a single bond. In the present embodiment,PFPE₁ and a group having a binding ability to the base material aredirectly bonded.

In still another embodiment, R^(k1) is a group represented by formula:—(R¹⁶)_(x)—(CFR¹⁷)_(y)—(CH₂)_(x)—. In the formula, x, y and z are eachindependently an integer of 0 to 10, the sum of x, y and z is 1 or more,and the occurrence order of the respective repeating units inparentheses is not limited in the formula.

In the formula, each R¹⁶, at each occurrence, independently representsan oxygen atom, phenylene, carbazolylene, —NR¹⁸—, wherein R¹⁸ representsa hydrogen atom or an organic group, or a divalent organic group.Preferably, R¹⁶ is an oxygen atom or a divalent polar group.

The “divalent polar group” is not limited, and examples thereof include—C(O)—, —C(═NR¹⁹)—, and —C(O)NR¹⁹—, wherein R¹⁹ represents a hydrogenatom or a lower alkyl group. The “lower alkyl group” is, for example, analkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethylgroup, or a n-propyl group, and such a group is optionally substitutedwith one or more fluorine atoms.

In the formula, each R¹⁷, at each occurrence, is independently ahydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferablya fluorine atom. The “lower fluoroalkyl group” is, for example, afluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbonatoms, preferably a perfluoroa1ky1 group having 1 to 3 carbon atoms,more preferably a trifluoromethyl group or a pentafluoroethyi group,further preferably a trifluoromethyl group.

In this embodiment, R^(k1) is preferably a group represented by formula:—(O)_(x)—(CF₂)_(y)—(CH₂)_(a)—, wherein x, y and z have the same meaningsas described above, and the occurrence order of the respective repeatingunits in parentheses is not limited in the formula.

Examples of the group represented by formula:—(O)_(x)—(CF₂)_(y)—(CH₂)_(z)— include any group represented by—(O)_(x′)—(CH₂)_(z′)—O—[(CH₂)_(z′′′)—O—]_(z′′), and—(O)_(x′)—(CF₂)_(y″)—(CH₂)_(x″)—O—[(CH₂)_(z′′′)—O—]_(x) _(x o) , whereinx′ is 0 or 1, y′, z′ and z′′′ are each independently an integer of 1 to10, and z″″ is 0 or 1. Herein, a left end of such a group is bonding toPFPE.

In another preferable embodiment, R^(k1) is —O—CFR²⁰—(CF₂)_(e′′′)—.

Each R²⁰ independently represents a fluorine atom or a lower fluoroalkylgroup. The lower fluoroalkyl group is, for example, a fluoroalkyl grouphaving 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1to 3 carbon atoms, more preferably a trifluoromethyl group or apentafluoroethyi group, further preferably a trifluoromethyl group.

Each e′′′ is independently 0 or 1.

In one specific example, R²⁰ is a fluorine atom and e′″ is 1.

In still another embodiment, examples of the R^(k1) group include thefollowing groups:

wherein

each R⁴¹ independently represents a hydrogen atom, a phenyl group, analkyl group having 1 to 6 carbon atoms or a C₁₋₆ alkoxy group,preferably a methyl group;

any number of the Ts in each R^(k1) group is the following group bondingto PFPE as a molecular backbone

-   —CH₂O(CH₂)₂—,-   —CH₂O(CH₂)₃—,-   —CF₂O(CH₂)₃—,-   —CH₂—,-   —(CH₂)₂—,-   —(CH₂)₃—,-   —(CH₂)₄—,-   —CONH—(CH₂)₃—,-   —CON(CH₃)—(CH₂)₃—,-   —CON(Ph)—(CH₂)₃—, wherein Ph means phenyl, or

wherein each R⁴² independently represents a hydrogen atom, a C₁₋₆ alkylgroup or a C₁₋₆ alkoxy group, preferably a methyl group or a methoxygroup, more preferably a methyl group,

-   another of the Ts is —(CH₂)_(n″)— (n″ is an integer of 2 to 6)    bonding to a group opposite to PFPE as a molecular backbone, and the    remaining of the Ts, if present, can be independently a methyl    group, a phenyl group, a C₁₋₆ alkoxy group, or a radical scavenging    group or an UV absorbing group.

The radical scavenging group is not limited as long as it can scavenge aradical generated by light irradiation, and examples thereof include aresidue of benzophenones, benzotriazoles, benzoates, phenyl salicylates,crotonic acids, malonates, organoacrylates, hindered amines, hinderedphenols, or triazines.

The UV absorbing group is not limited as long as it can absorbultraviolet light, and examples thereof include residue ofbenzotriazoles, hydroxybenzophenones, esters of substituted andunsubstituted benzoic acid or salicylic acid compounds, acrylates oralkoxy cinnamates, oxamides, oxanilides, benzoxazinones, andbenzoxazoles.

In a preferable embodiment, examples of a preferable radical scavenginggroup or an absorbing group include

In one embodiment examples of R^(k1) can include any group representedby —R^(k2)—CH₂—, —R^(k2)—OCH₂—, —R^(k2)—CH₂OCH₂—, or—R^(k2)—CO—NR¹—Y^(j2)—. A left portion of the formula of the divalentorganic group (namely, R^(k2) portion) is bonding to PFPE¹.

In the embodiment, R^(k2) is a single bond or a divalent hydrocarbongroup having 1 to 15 carbon atoms, and may contain an ether bond.Examples of the hydrocarbon group in R^(k2) can include an alkylenegroup or an alkylene group optionally containing ether oxygen. Thealkylene group is optionally substituted or unsubstituted, as describedabove.

In one embodiment, R^(k2) is a single bond. In another embodiment,examples of R^(k2) can include a divalent hydrocarbon group, preferablyan alkylene group where any hydrogen atom is at least partiallysubstituted with a fluorine atom, such as —CFH—, —CF₂—, —(CF₂)₂— or—(CF₂)₃—, specifically —CF₂—.

In the embodiment, Y^(j2) is —CH₂—, or an o, m orp-dimethylailylphenylene group represented by the following formula. Inthe following formula, a phenylene group is bonding to a N atom and a Siatom is bonding to a —CH═CH₂ group in formula (I), respectively.

In the embodiment, R¹ is a hydrogen atom or a substituted orunsubstituted monovalent hydrocarbon group. The substituted orunsubstituted monovalent hydrocarbon group is preferably a monovalenthydrocarbon group having 1 to 12 carbon atoms, more preferably amonovalent hydrocarbon group having 1to 10 carbon atoms. Specificexamples of such a substituted or unsubstituted monovalent hydrocarbongroup include alkyl groups such as a methyl group, an ethyl group, apropyl group, a butyl group, a hexyl group, a cyclohexyl group and an.octyl group; aryl groups such as a phenyl group and a tolyl group;aralkyl groups such as a benzyl group and a phenylethyl group, or amonovalent hydrocarbon group where some or all hydrogen atoms aresubstituted with a halogen atom such as a fluorine atom. R¹ ispreferably a hydrogen atom, a methyl group or a phenyl group.

In the embodiment, examples of the structure of a specificPFPE-containing compound (A) can include the following structures. Inthe following structures, PFPE¹ and R^(k2) have the same meanings asdescribed above.

The viscosity (25° C.) of PFPE-containing compound (A) is preferably inthe range from 5 to 100,000 mPa·s, more preferably in the range from 100to 10,000 mPa·s, further preferably in the range from 300 to 3,000mPa·s. The viscosity can be measured according to JIS K6249. ThePFPE-containing compound (A) having such a viscosity, when used forsealing, potting, coating, impregnation or the like, can contribute toformation of a cured product having proper physical characteristics. Therange of the viscosity of the PFPE-containing compound (A) can beappropriately selected within the range of the viscosity, depending onthe application.

The number average molecular weight of the PFPE-containing compound (A)is preferably in the range from 1,000 to 100,000, more preferably in therange from 2,000 to 20,000. The number average molecular weight of thePFPE-containing compound (A) can be any value measured by ¹⁹F-NMR.

The PFPE-containing compound (A) can be used singly or in combinationsof two or more kinds thereof.

The PFPE-containing compound (A) described above can be produced by aknown method or an improved method thereof.

The present invention is not limited to the following example, and, forexample, the PFPE-containing compound (A), when represented by thefollowing formula:

CH₂═CH—R^(k10)—NHC(═O)—PFPE¹-C(═O)NH—R^(k10)—CH═CH₂

wherein a —C(═O)NH—R^(k10)— portion corresponds to R^(k1), can besynthesized by reacting CH₃OC(═O)—PFPE¹-C(═O)OCH₃ and CH₂═CHR^(k10)NH₂.

In one embodiment, the PFPE-containing compound (A) includes no Si—Hbond in a molecular chain.

In one embodiment, the PFPE-containing compound (A) includes no Si atomin a molecular chain.

(Organosilicon Compound (B))

The organosilicon compound (B) has two or more hydrogen atoms eachbonding to a silicon atom (Si—H), in one molecule. The organosiliconcompound (B) can serve as a cross-linking agent or a chain extender ofthe PFPE-containing compound (A). The organosilicon compound (B) can beincluded, thereby improving physical properties (for example, tensilestrength and elastic modulus) of the curable composition of the presentinvention.

The Si—H is preferably present at an end of a molecular chain of theorganosilicon compound. (B).

The organosilicon compound (B) preferably has two or more silicon atomseach having a Si—H bond, in one molecule.

The organosilicon compound (B) preferably has a fluorine-containinggroup such as one or more monovalent perfluoroalkyl groups, monovalentperfluorooxyalkyl groups, divalent perfluoroalkylene groups or divalentperfluorooxyalkylene groups, in a molecular structure. Such a structurecan be contained to thereby improve miscibility and dispersibility ofthe organosilicon compound (B) and the PFPE-containing compound (A)included in the curable composition of the present invention, and alsoimprove uniformity of a cured product of the curable composition of thepresent invention.

The number of carbon atoms in the monovalent perfluoroalky1 group ispreferably 1 to 20, more preferably 2 to 10. The perfluoroalkyl groupmay be linear or branched, and is preferably linear.

The monovalent, perfluorooxyalkyl group is preferably a grouprepresented by Rf—PFPE²—. PFPE² is represented by formula:

—(OC₆F₁₂)_(a″)—(OC₅F₁₀)_(b″)—(OC₄F₈)_(c″)—(OC₃F₆)_(d″)—(OC₂F₄)_(e″)—(OCF₃)_(f″)—,

PFPE² may be linear or branched, and is preferably linear.

In the formula, a″, b″, c″ and d″ are each independently an integer of 0or more and 30 or less, e″ and f″ are each independently an integer of 1or more and 200 or less. Preferably, the sum of a″, b″, c″, d″, e″ andf″ is 5 or more, more preferably 10 or more, for example, 10 or more and200 or less. The occurrence order of the respective repeating units inparentheses with the subscript a41 , b″, c″, d″, e″ or f″ is not limitedin the formula. The ratio of e″ to f″ is 1.0 or more.

Here, a″, b″, c″, d″, e″ and f″ can have the same meanings as a, b, c,d, e and f of PFPE¹, respectively. Examples of specific structures ofthe respective repeating units contained in PFPE² can include thoseexemplified as the respective repeating units of PFPE¹.

Preferably, PFPE² is—(OC₄P₈)_(c″)—(OC₃F₆)_(d″)—(OC₂F₄)_(e″)—(OCF₂)_(f″)—, wherein c″ and d″are each independently an integer of 0 or more and 30 or less, e″ and f″are each independently an integer of 1 or more and 200 or less,preferably 5 or more and 200 or less, more preferably 10 or more and 200or less, and the occurrence order of the respective repeating units Inparentheses with the subscript c″, d″, e″ or f″ is not limited in theformula. Preferably, PFPE² is—(OCF₂CF₂CF₂CF₂)_(c″)—(OCF₂CF₂CF₂)_(d″)—(OCF₂CF₂)_(e″)—(OCF₂)_(f″)—. Inone embodiment, PFPE² may be —(OC₂F₄)_(e″)—(OCF₂)_(f″)—, wherein e″ andf″ are each independently an integer of 1 or more and 200 or less,preferably 5 or more and 200 or less, more preferably 10 or more and 200or less, and the occurrence order of the respective repeating units inparentheses with the subscript e″ or f″ is not limited in the formula.

In the formulae, each Rf, at each occurrence, independently represents achlorine atom, a fluorine atom, or an alkyl group having 1 to 16 carbonatoms, the group being optionally substituted with one or more fluorineatoms or chlorine atoms.

The “alkyl group having 1 to 16 carbon atoms” with respect to the alkylgroup having 1 to 16 carbon atoms, the group being optionallysubstituted with one or more fluorine atoms, is optionally linear orbranched, is preferably a linear or branched alkyl group having 1 to 6carbon atoms, particularly 1 to 3 carbon atoms, more preferably a linearalkyl group having 1 to 3 carbon atoms.

Rf is preferably a fluorine atom, or an alkyl group having 1 to 16carbon atoms, the group being optionally substituted with one or morefluorine atoms, more preferably a CF₂H—C₁₋₁₅ fluoroalkylene group or aC₁₋₁₆ perfluoroalkyl group, further preferably a C₁₋₁₆ perfluoroalkylgroup.

The perfluoroalkyl group having 1 to 16 carbon atoms may be linear orbranched, and is preferably a linear or branched perfluoroalkyl grouphaving 1 to 6 carbon atoms, in particular, 1 to 3 carbon atoms, morepreferably a linear perfluoroalkyl group having 1 to 3 carbon atoms,specifically —CF₃, —CF₂CF₃, or —CF₂CF₂CF₃.

Preferably, the monovalent perfluorooxyalkyl group isRf—(OC₂F₄)_(e″)—(OCF₂)_(f″)—, wherein e″ and f″ are each independentlyan integer of 1 or more and 200 or less, preferably 5 or more and 200 orless, more preferably 10 or more and 200 or less, and the occurrenceorder of the respective repeating units in parentheses with thesubscript e″ or f″ is not limited in the formula.

The ratio of e″ to f″ in the monovalent perfluorooxyalkyl group ispreferably 1.0 or more, more preferably 1.1 or more, further preferably1.2 or more, and preferably 10.0 or less, more preferably 5.0 or less,further preferably 2.0 or less, particularly preferably 1.5 or less.

The ratio of e″ to f″ in the monovalent perfluorooxyalkyl group ispreferably 1.0 or more and 10.0 or less, more preferably 1.0 or more and5.0 or less, further preferably 1.0 or more and 2.0 or less,particularly preferably 1.0 or more and 1.5 or less.

The number of carbon atoms in the divalent perfluoroalkylene group ispreferably 1 to 20, more preferably 2 to 10. The perfluoroalkylene groupmay be linear or branched, and is preferably linear.

The divalent perfluorooxyalkylene group is preferably represented by—PFPE²—, and is more preferably a group represented by—(OC₄F₈)_(c″)—(OC₃F₆)_(d″)—(OC₂F₄)_(e″)—(OCF₂)_(f″)—. Here, c″, d″, e″,and f″ have the same meanings as described above. The perfluorooxyalkylgroup may be linear or branched, and is preferably linear. PFPE² has thesame meaning as described above.

The fluorine-containing group is preferably the monovalentperfluoroalkyl group or the divalent perfluoroalkylene group.

The fluorine-containing group and a silicon atom may be connected by adivalent organic group. The divalent organic group has the same meaningas described above.

For example, the divalent organic group may be any of an alkylene group,an arylene group, and a combination thereof, or may be such a group withan ether bond oxygen atom, an amide bond, a carbonyl bond, or the likeinterposed. Examples of such a divalent organic group include groupshaving 2 to 12 carbon atoms, such as

-   —CH₂CH₂—,-   —CH₂CH₂CH₂—,-   —CH₂CH₂CH₂OCH₂—,-   —CH₂Ch₂CH₂—NH—CO—,-   —CH₂Ch₂CH₂—N (Ph)—CO— (provided that Ph is a phenyl group.),-   —CH₂CH₂CH₂—N(CH₃)—CO—,-   —CH₂CH₂CH₂—O—CO—. A left portion of the divalent organic group is    bonding to a Si atom and a right portion of the divalent organic    group is bonding to a fluorine-containing group, respectively.

In the organosilicon compound (B), examples of any group which is amonovalent substituent bonding to a silicon atom and which is other thanthe fluorine-containing group include substituted or unsubstitutedhydrocarbon groups each having 1 to 20 carbon atoms such as alkyl groupssuch as a methyl group, an ethyl group, a propyl group, a butyl group, ahexyl group, a cyclohexyl group, an octyl group and a decyl group;alkenyl groups such as a vinyl group and an allyl group; aryl groupssuch as a phenyl group, a tolyl group and a naphthyl group; aralkylgroups such as a benzyl group and a phenylethyl group, and a groupthereof where at least some or all hydrogen atoms of such a group aresubstituted with a chlorine atom, a cyano group or the like, such as achloromethyl group, a chloropropyl group and a cyanoethyl group.

Preferably, the organosilicon compound (B) does not have any alkoxygroup and epoxy group as a substituent bonding to a silicon atom.

The organosilicon compound (B) may be a cyclic, linear orthree-dimensional network compound, or a combination thereof.

The number of silicon atoms included in the organosilicon compound (B)is not limited, and can be usually 2 to 60, preferably about 3 to 30.

Examples of the organosilicon compound (B) can include the followingcompounds. Such a compound may be used singly or in combinations of twoor more kinds thereof.

In the following formulae:

each PFPE², at each occurrence, independently has the same meaning asdescribed above (in the following formulae, a group represented by PFPE²is bonding to a group represented by Rf on an oxygen atom at an end);

each Rf, at each occurrence, independently has the same meaning asdescribed above;

each R^(k3), at each occurrence, is independently an alkyl group having1 to 10 carbon atoms or an alkoxy group represented by OR^(k7),preferably a methyl group or an alkoxy group represented by OR^(k7),more preferably a methyl group;

each R^(k4), at each occurrence, is independently a hydrogen atom, analkyl group having 1 to 10 carbon atoms or an alkoxy group representedby OR_(k7), preferably a hydrogen atom or an alkoxy group represented byOR^(k7), more preferably a hydrogen atom;

each R^(k5), at each occurrence, is independently a hydrogen atom, analkyl group having 1 to 10 carbon atoms or an alkoxy group representedby OR^(k7), preferably a hydrogen atom or an alkoxy group represented byOR^(k7), more preferably a hydrogen atom;

each R^(k6), at each occurrence, is independently a hydrogen atom, afluorine atom, or an alkylene group where one or more hydrogen atoms areeach substituted with a fluorine atom, preferably a hydrogen atom;

each R^(k7), at each occurrence, .is independently an alkyl group having1 to 10 carbon atoms, preferably an alkylene group having 1 to 6 carbonatoms;

the number of carbon atoms contained in the alkylene group where one ormore hydrogen atoms are each substituted with a fluorine atom ispreferably 1 to 8, more preferably 1 to 6;

R^(k8) is represented by —(O—(Ch₂)_(α5))_(α6)— (where an oxygen atom isbonding to a group represented by —(CR^(k6) ₂)_(α1));

each α1, at each occurrence, is independently an integer of 1 to 10,preferably 2 or 3;

each 2, at each occurrence, is independently an integer of 1 to 50,preferably 10;

each α3, at each occurrence, s independently an integer of 1 to 50,preferably an integer of 3 to 5;

each α4, each occurrence, is independently an integer of 1 to 50,preferably an integer of 3 to 5;

each α5 is an integer of 1 to 5, preferably 1 to 3, more preferably 1;and

α6 is 0 or 1.

The content of the organosilicon compound (B) can be an amount effectivefor curing the PFPE-containing compound (A). The content of theorganosilicon compound (B) is preferably in the range from 0.5 to 5.0mol, more preferably in the range from 0.8 to 3.0 mol in terms of ahydrogen atom bonding to a silicon atom contained in the organosiliconcompound (B) (hydrosilyl group, namely, Si.H group) based on 1 mol of analkenyl group contained in the PFPE-containing compound (A). The curablecomposition of the present invention can include such a content of theorganosilicon compound (B) to thereby contribute to formation of a curedproduct having an appropriate degree of cross-inking, and preventfoaming when it is cured.

(Catalyst (C))

The curable composition. of the present invention further includes acatalyst (hereinafter, sometimes referred to as “catalyst (C)”). Thecatalyst (C) can serve as a hydrosilylation reaction catalyst. Such ahydrosilylation reaction catalyst promotes an addition reaction of analkenyl group in the PFPE-containing compound (A) and a hydrogen atombonding to a silicon atom (hydrosilyl group) in the organosiliconcompound (B).

The catalyst (C) here used is preferably a transition metal catalyst.The transition metal contained in the catalyst (C) is preferably atleast one selected from the group consisting of platinum, rhodium,ruthenium, iridium and palladium.

Platinum or a platinum compound is preferably used as the catalyst (C) .Such a catalyst (C) has the advantages of a reduction in catalyst costand catalyst availability.

Examples of the platinum compound can include hydrogen chloroplatinateor a complex of hydrogen chloroplatinate and olefin such as ethylene, acomplex thereof with alcohol or vinylsiloxane, and metallic platinumcarried on silica, alumina, carbon or the like.

Examples of the catalyst containing rhodium, ruthenium, iridium orpalladium can include RhCl(PPh₃)₃, RhCl(CO) (PPh₃)₂, Ru₃(CO)₁₂, IrCl(CO)(PPh₃)₂ and Pd(PPh₃)₄. In the formulae, Ph is a phenyl group.

The catalyst (C) can be used in the form of a solid when the catalyst isa solid, and hydrogen chloroplatinate or a complex, dissolved in aproper solvent, is preferably used with being miscible with thePFPE-containing compound (A) in order to provide a more uniform curedproduct.

The catalyst may be included in the curable composition of the presentinvention in an effective amount so as to be able to contribute to areaction, for example, in an effective amount so as to be able tocontribute to a reaction with serving as a hydrosilylation reactioncatalyst. The content of the catalyst can be appropriately increased ordecreased depending on a desired curing rate. The content of thecatalyst is usually preferably 0.1 to 500 ppm by mass (in terms of metalatom) relative to the PFPE-containing compound (A).

(Organosilicon Compound (D))

The curable composition of the present invention can further include anorganosilicon compound which has one or more hydrolyzable groups eachbonding to a silicon atom in one molecule (hereinafter, sometimesreferred to as “organosilicon compound (D)”). The organosilicon compoundwhich has one or more hydrolyzable groups each bonding to a silicon atomin one molecule can serve as an adhesion-imparting agent which canimpart self-adhesiveness in the composition.

The “hydrolyzable group” herein means a group which can undergo ahydrolysis reaction, namely, means a group which can be removed from amain backbone of the compound in a hydrolysis reaction. Examples of thehydrolyzable group include —OR, —OCOR, —O—N═CR₂, —NR₂, —NHR and halogen,wherein R represents a substituted or unsubstituted alkyl group having 1to 4 carbon atoms, and —OR (namely, an alkoxy group) is preferable andan alkoxy group is more preferable. Examples of R include unsubstitutedalkyl groups such as a methyl group, an ethyl, group, a propyl group, anisopropyl group, a n-butyl group and an isobutyl group; and substitutedalkyl groups such as a chloromethyl group. Among them, an alkyl group,in particular, an unsubstituted alkyl group is preferable, and a methylgroup or an ethyl group is more preferable. The hydroxyl group is notlimited, and, may be generated by hydrolyzing the hydrolyzable group.Examples of the halogen can include a. fluorine atom, a chlorine atom, abromine atom and an iodine atom, and in particular, a chlorine atom ispreferable.

The organosilicon compound (D) may be used singly or in combinations oftwo or more kinds thereof.

The organosilicon compound (D) may have one or more monovalentperfluoroalkyl groups or monovalent perfluorooxyalkyl groups. Such astructure can be contained to thereby particularly improve raiscibilityand dispersibility of the organosilicon compound (D) and thePFPE-containing compound (A) contained in the curable composition, andimprove uniformity of a cured product of the curable composition.

The organosilicon compound (D) may have one or more hydrogen atoms eachbonding to a silicon atom in one molecule from the viewpoint of additionreactivity with the PFPE-containing compound (A).

The organosilicon compound (D) is preferably organosiloxane ortrialkoxysilane having one or more alkoxysilyl groups each bonding to asilicon atom via a carbon atom or a carbon atom and an oxygen atom.

The siloxane backbone of the organosiloxane in the organosiliconcompound (D) may be a cyclic, linear or branched backbone, or acombination thereof. The organosiloxane can be the organosiloxanerepresented by the following general formula.

In the general formulae, each j1, at each occurrence, is preferablyindependently an integer of 0 to 50, more preferably an integer of 0 to20. In the general formulae, each j2, at each occurrence, is preferablyindependently an integer of 0 to 50, more preferably an integer of 0 to20. In the general formulae, each j3, at each occurrence, is preferablyindependently an integer of 1 to 50, more preferably an integer of 1 to20. In the general formulae, each j4, at each occurrence, is preferablyindependently an integer of 0 to 50, more preferably an integer of 0 to20. In the general formulae, each j5, at each occurrence, is preferablyindependently an integer of 0 to 50, more preferably an integer of 0 to20. The sum of j1, j2, j3, j4 and j5 is an integer which allows theweight average molecular weight in terms of polystyrene according to gelpermeation chromatography (GPC) to satisfy 500 to 20,000.

In the general formulae, each R^(j1), at each occurrence, isindependently a halogen-substituted or unsubstituted monovalenthydrocarbon group. The number of carbon atoms contained in thehalogen-substituted or unsubstituted monovalent hydrocarbon group ofR^(j1) is preferably in the range from 1 to 10, more preferably in therange from 1 to 6. Specific examples of such a monovalent hydrocarbongroup can include alkyl groups such as a methyl group, an ethyl group, apropyl group, a butyl group, a hexyl group, a cyclohexyl group and anoctyl group; aryl groups such as a phenyl group and a tolyl group;aralkyl groups such as a benzyl group and a phenylethyl group, or asubstituted monovalent hydrocarbon group where some or all hydrogenatoms of these groups are substituted with a halogen atom such as afluorine atom. In particular, the monovalent hydrocarbon group is morepreferably a methyl group.

In the general formulae, R^(j2) represents an alkoxysilyl group bondingto a silicon atom via a carbon atom or a carbon atom and an oxygen atom,and specific examples thereof include

—R^(j5)—Si(OR^(j6))₃, or a group represented by the following formula.

In the formulae, R^(j5) is a divalent hydrocarbon group having 1 to 10carbon atoms, in particular, 1 to 4 carbon atoms, specifically, analkylene group such as a methylene group, an ethylene group, a propylenegroup, a butylene group, a hexylene group, a cyclohexylene group or anoctylene group, and R^(j6) is a monovalent hydrocarbon group having 1 to8 carbon atoms, in particular, 1 to 4 carbon atoms, specifically, forexample, an alkyl group such as a methyl group, an ethyl group or an-propyl group. R^(j7) is a monovalent hydrocarbon group having 1 to 8carbon atoms, in particular, 1 to 4 carbon atoms, specifically, an alkylgroup such as a methyl group, an ethyl group or a n-propyl group, R^(j8)is a hydrogen atom or a methyl group, and k is an integer of 2 to 10.

In the general formulae, R^(j3) is a group represented by the followinggeneral formula:

—Z^(j1)—Rf^(j1).

Herein, a right portion of Z^(j1) is bonding to Rf^(j1).

In the formula, Z^(j1) is a group represented by —(CH₂)_(j6)—,—(CH₂)_(j7)—X^(j1)—, wherein X^(j1) is —OCH₂—, or —Y^(j1)—NR^(j9)—CO—,wherein Y^(j1) is —CH₂— or an o, m or p-dimethylsilylphenylenerepresented by the following structural formula:

wherein a phenylene group is bonding to a N atom, and R^(j9) is ahydrogen atom, or a substituted or unsubstituted monovalent hydrocarbongroup preferably having 1 to 12 carbon atoms, in particular, 1 to 10carbon atoms, and j6 and j7, at each occurrence, are each independentlyan integer of 1 to 10, preferably an integer of 1 to 5. In the formulae,Rf^(j1) represents a monovalent perfluoroalkyl group or a monovalentperfluorooxyalkyl group.

The monovalent perfluoroalkyl group or the monovalent perfluorooxyalkylgroup has the same meaning as described above.

R^(j4) is an epoxy group bonding to a silicon atom via a carbon atom ora carbon atom and an oxygen atom, and specific examples thereof caninclude the following groups:

wherein R^(j10) is a divalent hydrocarbon group having 1 to 10 carbonatoms, in particular, 1 to 5 carbon atoms, optionally with an oxygenatom interposed, specifically, an alkylene group such as a methylenegroup, an ethylene group, a propylene group, a butylene group, ahexylene group, a cyclohexylene group or an octylene group.

Specific examples of the organosiloxane used as the organosiliconcompound (D) include any organosiloxane represented by the followingstructural formula. In the following, a group represented by PFPE² isbonding to a group represented by Rf, on an oxygen atom at an end.

In the formulae, Me represents a methyl group, and p, q and r, at eachoccurrence, are each independently an integer of 0 or more. PFPE² and Rfhave the same meanings as described above.

The trialkoxysilane used as the organosilicon compound (D) is notlimited, and is preferably any silane having a reactive organic groupother than an alkoxy group in the same molecule, such asvinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane,3-glycidoxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane,3-(methacryloxypropyl)trimethoxysilane,2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,N-2-(aminoethyl)-3-aminopropyltrimethoxysilane,N-phenyl-3-aminopropyltrimethoxysilane,3-isocyanatopropyltriethoxysilane, or fluorine-containingtrialkoxysilane such as perflucropropyltrimethoxysilane.

The amount of the organosilicon compound (D) compounded is preferably inthe range from 0.01 to 10 parts by mass, more preferably in the rangefrom 0.05 to 5 parts by mass based on 100 parts by mass of thePFPE-containing compound (A). The organosilicon compound (D) can beincluded in the range to thereby allow the curable composition to havesufficient adhesiveness and have appropriate fluidity and curability.Such a curable composition can be favorable in physical hardness.

(Hydrolysis Catalyst)

The curable composition of the present invention can further include ahydrolysis catalyst (hereinafter, sometimes referred to as “hydrolysiscatalyst (E)”). The hydrolysis catalyst has a catalyst function forenhancing hydrolyzability of the organosilicon compound (D).

The hydrolysis catalyst is not limited as long as the catalyst does notimpair addition curability of the composition, and examples thereofinclude organotitanium compounds such as titanium tetraisopropoxide,titanium tetra-n-butoxide and titanium tetraacetylacetonate;organozirconium compounds such as zirconium tetra-n-propoxide, zirconiumtetra-n-butoxide and zirconium tetraacetylacetonate; organotin compoundssuch as dibutyltin dilaurate, dibutyltin diacetate and dibutyltinacetylacetonate; organoaluminum compounds such as aluminumtrisacetylacetonate, aluminum trisethylacetoacetate and diisopropoxyaluminum ethylacetoacetate; and other acidic catalysts and basiccatalysts. In particular, at least one selected from the groupconsisting of such organotitanium compounds, organozirconium compounds,organotin compounds and organoaluminum compounds is preferably used fromthe viewpoint of storage stability of the curable composition of thepresent invention. The hydrolysis catalyst may be used singly or incombinations of two or more kinds thereof.

The amount of the hydrolysis catalyst compounded is preferably in therange from 0.001 to 5 parts by mass. more preferably in the range from0.01 to 1 part by mass based on 100 parts by mass of the PFPE-containingcompound (A). The hydrolysis catalyst can be included in the range inthe curable composition of the present invention, thereby exerting asufficient catalyst effect. The hydrolysis catalyst can be included inthe range, thereby allowing the curable composition of the presentinvention to have appropriate fluidity. The hydrolysis catalyst can alsobe prevented from being cured into a gel.

(Component (F))

Various additives can be, if necessary, added to the curable compositionof the present invention in order to enhance practicality of thecomposition. For example, organosiloxane (hereinafter sometimes referredto as “component (F)”) can be added which acts as an adhesion-impartingagent and which has one or more epoxy groups each bonding to a siliconatom via a carbon atom or a carbon atom and an oxygen atom and no alkoxygroup in one molecule.

The component (F) is more preferably one having one or more monovalentperfluoroalkyl groups or monovalent perfluorooxyalkyl groups eachbonding to a silicon atom via a carbon atom bonding to a silicon atom orvia a carbon atom and an oxygen atom from the viewpoint of miscibilityarid dispersibility with PFPE-containing compound (A), uniformity aftercuring of the curable composition, and the like.

The component (F) may have one or more hydrogen atoms each directlybonding to a silicon atom in one molecule from the viewpoint of additionreactivity with the PFPE-containing compound (A) .

The siloxane backbone cf the organosiloxane of the component (F) can bethe same as organosiloxane which can be used as the organosiliconcompound (D), and may be a cyclic, linear or branched backbone, or acombination thereof.

The organosiloxane of the component (F) can be organosiloxanerepresented by the following general formula.

In the formulae, R^(j1), R^(j6), R^(j3), R^(j4), j1, j2, j3 and j4 havethe same meanings as described above.

Specific examples of the organosiloxane used in the component (F)include any organosiloxane represented by the following structuralformula. Such a compound may be used singly or in combinations of two ormore kinds thereof. In the following formulae, Me represents a methylgroup, and p, q and r is an integer of 0 or more. Rf″ has the samemeaning as Rf, and is preferably a fluorine atom. Hereinafter, a grouprepresented by PFPE² is bonding to a group represented by Rf″, on anoxygen atom at an end.

The amount of the component (F) compounded is preferably in the rangefrom 0.01 to 10 parts by mass, more preferably in the range from 0.1 to5 parts by mass based on 100 parts by mass of the PFPE-containingcompound (A). The component (F) can be included in such an amount,thereby allowing the curable composition of the present invention tohave particularly sufficient adhesiveness and also allowing the curablefavorable in fluidity. The component (F) can be included in such anamount, thereby also allowing the curable composition of the presentinvention to be favorable in physical strength.

(Other Component)

The curable composition of the present invention may be used togetherwith a solvent. In such a case, the curable composition can be used,with being dissolved in a proper fluorine-based solvent so as to have adesired concentration depending on the application and the intended use.The concentration of the fluorine-based solvent may be, for example, 300parts by mass or less, 100 parts by mass or less, or 50 parts by mass orless based on 100 parts by mass of the curable composition. When thecurable composition and the solvent are used as a mixture, the viscosityof the mixture can be adjusted. When the curable composition is usedwith the solvent, the handleability of the mixture can be well.Additionally, it may be easy to control the shape of a cured productformed from the curable composition, and, for example, it may be easy toform a cured product in large thickness. When the curable composition isused as the mixture, it may be easy to use the mixture in sprayprocessing or dip processing, and then the degree of freedom in aprocessing step can be increased.

The solvent here used can also be any fluorine-based solvent selectedfrom the group consisting of perfluorohexane, CF₃CF₃CHCl₂, CF₃CH₂CF₂CH₃,CF₃CHFCHFC₂F₅, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane,1,1,2,2,3,3,4-heptafluorocyclopentane ((Zeorora H (trade name) or thelike), C₄F₉OCH₃, C₄F₃OC₂H₅, CF₃CH₂OCF₂CHF₂, C₆F₁₃CH═CH₂, xylenehexafluoride, perfluorobenzene, methylpentadecafluoroheptylketone,trifluoroethanol, pentafluoropropanol, hexafluoroisopropanol,HCF₂CF₃CH₂OH, methyltrifluoromethanesulfonate. trifluoroacetic acid,CF₃O(CF₂CF₂ 0)_(m1)(CF₂O)_(n1)CF₂CF₃, wherein m1 and n1 are eachindependently an integer of 0 or more and 1000 or less and theoccurrence order of the respective repeating units in parentheses withm1 or n1 is not limited in the formula, provided that the sum of m1 andn1 is 1 or more, 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene,1,2-dichloro-1,3,3,3-tetrafluoro-1-propene,1,2-dichloro-3,3,3-trifluoro-1-propene,1,1-dichloro-3,3,3-trifluoro-1-propene,1,1,2-trichloro-3,1,3-trifluoro-1-propene,1,1,1,4,4,4-hexafluoro-2-butene, 1,3-bis(trifluoromethyl)benzene.Fluorinert (manufactured by 3M), perfluorobutyl methyl ether, andperfluorobutyl ethyl ether.

The curable composition of the present invention may further includeother component. Such other component is not limited, and may include,for example, various additives such as a (non-reactive) fluoropolyethercompound which can be understood as a fluorine containing oil,preferably a perfluoro(poly)ether compound (hereinafter, referred to as“fluorine-containing oil”), a stabilizing material (dehydrating agent,molecular sieve, magnesium sulfate or methyl orthoformate), a viscositymodifier, a filler, a fluorescent agent, a storage stabilizer, a fillingagent, a colorant, a heat resistance improved, a cold resistanceimproved, a rust inhibitor, an adhesiveness improved, a liquidstrengthening agent, a plasticizer, a viscosity modifier, aflexibility-imparting agent and an adhesion promoter.

The amount of such an additive compounded is not limited as long as theobject of the present invention is not impaired and characteristics ofthe composition and physical properties of a cured product are notimpaired.

The fluorine-containing oil is not limited, and examples thereof includea compound (perfluoro(poly)ether compound) represented by the followinggeneral formula (III):

Rf⁵—(OC₄F₈)_(a′)—(OC₃F₆)_(b′)—(OC₂F₄)_(c′)—(OCF₂)_(d′)—Rf⁶   (III)

wherein Rf₅ represents an alkyl group having 1 to 16 carbon atomsoptionally substituted with one or more fluorine atoms (preferably C₁₋₁₆perfluoroalkyl group), Rf⁶ represents an alkyl group having 1 to 16carbon atoms optionally substituted with one or more fluorine atoms(preferably C₁₋₁₆ perfluoroalkyl group), a fluorine atom or a hydrogenatom, and Rf⁵ and Rf⁶ are more preferably, each independently, a C₁₋₃perfluoroalkyl group; and

a′, b′, c′ and d′ represent the respective four numbers of repeatingunits in perfluoro(poly)ether constituting a main backbone of thepolymer and are mutually independently an integer of 0 or more and 300or less, the sum of a′, b′, c′ and d′ is at least 1, preferably 1 to300, more preferably 20 to 300, the occurrence order of the respectiverepeating units in parentheses with the subscript a′, b′, c′ or d′ notlimited in the formula, and , among such repeating units, —(OC₄F₈)— maybe any of —(OCF₂CF₂CF₂CF₂)—, —(OCF(CF₃)CF₂CF₂)—, —(OCF₂CF(CF₃)CF₂)—,—(OCF₂CF₂CF(CF₃))—, —(OC(CF₃)₂CF₂)—, —(OCF₂C(CF₃)₂)—,—(OCF(CF₃)CF(CF₃))—, —(OCF(C₂F₅)CF₂)— and —(OCF₂CF(C₂F₅))—, and ispreferably —(OCF₂CF₂CF₂CF₂)— and —(OCF₂CF(CF₃))—, and is preferably—(OCF₂CF₂CF₂)—, and, for example, —(OC₂F₆)— may be any of —(OCF₂CF₂)—and —(OCF(CF₃))—, and is preferably —(OCF₂CF₂)—.

Examples of the perfluoro(poly)ether compound represented by generalformula (III) include a compound represented by any of the followinggeneral formulae (IIIa) and (IIIb) (which may be adopted singly or as amixture of two or more kinds thereof).

Rf⁵—(OCF₂CF₂CF₂)_(b′′)—Rf⁶   (IIIa)

Rf⁵—(OCF₂CF₂CF₂CF₂)_(a′′)—(OCF₂CF₂CF₂)_(b′′)—(OCF₂CF₂)_(c′′)—(OCF₂)_(d′′)—Rf⁶  (IIIb)

In such formulae, Rf⁵ and Rf⁶ are as described above; in formula (IIIa),b′′ is an integer of 1 or more and 100 or less; in formula (IIIb), a′′and b′′ are each independently an integer of 1 or more and 30 or less,and c′′ and d′′ are each independently an integer of 1 or more and 300or less, and the occurrence order of the respective repeating units inparentheses with subscript a′′, b′′, c′′, d′′ is not limited in theformulae.

The fluorine-containing oil may have a number average molecular weightof 1,000 to 30,000. In particular, the number average molecular weightof the compound represented by formula (IIIa) is preferably 2,000 to8,000. In one embodiment, the number average molecular weight of thecompound represented by formula (IIIb) is 3,000 to 8,000. In anotherembodiment, the number average molecular weight of the compoundrepresented by formula (IIIb) is 8,000 to 30,000.

The curable composition can contain, for example, 0 to 500 parts bymass, preferably 0 to 100 parts by mass, more preferably 1 to 50 partsby mass, further preferably 1 to 5 parts by mass of thefluorine-containing oil based on 100 parts by mass of thePFPE-containing compound (A).

The fluorine-containing oil may be a compound represented by generalformula Rf′—F, wherein Rf′ is C₅₋₁₆ perfluoroalkyl group, from anotherviewpoint. The fluorine-containing oil may be a chlorotrifluoroethyleneoligomer.

The curable composition can include such a fluorine-containing oil to bethereby formed into a more flexible curing composition.

In one embodiment, the average molecular weight of thefluorine-containing oil may be higher than the average molecular weightof the PFPE-containing compound (A) (for example, a compound representedby formula (I)). Such an average molecular weight can be set to therebyallow a cured product formed by using the curable composition of thepresent invention to achieve more excellent friction durability andsurface lubricity.

In one embodiment, the average molecular weight of thefluorine-containing oil may be lower than the average molecular weightof the PFPS-containing compound (A) (for example, a compound representedby formula (I)). Such an average molecular weight can be set to therebyallow the curable composition of the present invention to not only beinhibited from being reduced in transparency of a cured product formedby using the curable composition, but also contribute to formation of acured product having high friction durability and high surfacelubricity.

Examples of the storage stabilizer can include methyltrimethoxysilane,methyltripropenoxysilane, vinyltributanoximesilane andmethyltriacetoxysilane.

Examples of the filler can include aerosol silica, precipitated silica,titanium dioxide, aluminum oxide, quartz powder, carbon powder, mica,clay, talc and bentonite. The filler, which can be further added, is,for example, fumed silica, colloidal silica, a quartz powder, a fusedquartz powder, diatomaceous earth, calcium carbonate or the like (theamount compounded is preferably 0.1 to 50 parts by mass, more preferably1 to 25 parts by mass based on 100 parts by mass of the PFPE-containingcompound (A).); an inorganic pigment such as titanium oxide, iron oxide,carbon black or cobalt aluminate; a heat resistance improved such astitanium oxide, iron oxide, carbon black, cerium oxide, ceriumhydroxide, zinc carbonate, magnesium carbonate or manganese carbonate;or a thermal conductivity-imparting agent such as alumina, boronnitride, silicon carbide or a metal powder.

Examples of the filling agent can include fibrous filling agents such asasbestos, glass fiber and an organic fiber.

Examples of the colorant can include a pigment and a dye.

Examples of the heat resistance improved can include colcothar andcerium oxide.

Examples of the adhesiveness improved can includeβ-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane,γ-methacryloxypropylmethyldiethoxysilane,N-β-(aminoethyl)-γ-aminopropyltrimetboxysilane,γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane,γ-mercaptopropyltrimethoxysilane and γ-isocyanatopropyltriethoxysilane.

Examples of the liquid strengthening agent can include reticularpolysiloxane having a triorganosiloxy unit and a SiO₂ unit.

Examples of a controlling agent of the hydrosilylation reaction catalystinclude acetylenic alcohol such as 1-ethynyl-1-hydroxycyclohexane,3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-penten-3-olor phenylbutynol, a reaction product of chlorosilane having themonovalent fluorine-containing substituent with such an acetylenicalcohol, 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, triallylisocyanurate, polyvinylsiloxane, or an organophosphorus compound, andaddition of such a compound enables curing reactivity and storagestability to toe properly kept.

The plasticizer, viscosity modifier and flexibility-imparting agent hereused can be each a compound represented toy:

Rf—PFPE²—R^(k1)—CH═CH₂

wherein:

Rf represents an alkyl group having 1 to 16 carbon atoms, optionallysubstituted with one or more fluorine atoms (preferably, C₁₋₁₆perfluoroalkyl group), a fluorine atom, or a hydrogen atom, preferably aC₁₋₃ perfiuoroalkyl group, more preferably a linear perfIuoroalkyl grouphaving 1 to 3 cartoon atoms, specifically, —CF₃, —CF₂CF₃ or —CF₂CF₂CF₃;

PFPE² has the same meaning as described above;

a group represented by PFPE² is bonding to a group represented by Rf, onan oxygen atom at an end; and

R^(k1) has the same meaning as described above, and is preferably

-   a single bond,-   —CH₂—O—CH₂—,-   —C(═O)—NHCH₂—,-   —C(═O)—N(Ph)—CH₂—,-   —C(═O)—NHPh—Si(CH₃)₂—, or-   —C(═O)—N(CH₃)Ph—Si(CH₃)₂—, wherein Ph represents a phenyl group.

In one embodiment, the curable composition of the present inventionincludes 0.1% by moi or more and 35% by mol or less of a compoundrepresented by formula:

Rf—PFPE²—R^(k1)—CH═CH₂

(hereinafter, also referred to as “component (2)”) based on the total ofthe compound represented by formula (I) (hereinafter, also referred toas “component (1)”) and the component (2). The lower limit of thecontent of the component (2) based on the total of the component (1) andthe component (2) is preferably 0.1% by mol, more preferably 0.2% bymol, further preferably 0.5% by mol, still more preferably 1% by mol,particularly preferably 2% by mol, and can be specially 5% by mol. Theupper limit of the content of the component (2) based on the total ofthe component (1) and the component (2) is preferably 35% by mol, morepreferably 30% by mol, further preferably 20% by mol, still morepreferably 15% by mol, or can be 10% by mol. The content of thecomponent (2) based on the total of the component (1) and the component(2) is preferably 0.1% by mol or more and 30% by mol or less, morepreferably 0.1% by mol or more and 20% by mol or less, furtherpreferably 0.2% by mol or more and 10% by mol or less, still morepreferably 0.5% by mol or more and 10% by mol or less, particularlypreferably 1% by mol or more and 10% by mol or less, for example, 2% bymol or more and 10% by mol or less or 5% by mol or more and 10% by molor less. The contents of component (1) and the component (2) can be insuch ranges to thereby allow the curable composition of the presentinvention to contribute to formation of a cured product favorable infriction durability.

An adhesion promoter such as carboxylic anhydride or pyromellitic acidtetraallyl ester can be further added to the curable composition of thepresent invention.

For example, such a composition may be configured as one-liquid typecomposition where all the components designated as (A) to (E) and thecomponent (F) and other any component are assumed to be one compositionor may be configured as a two-liquid type composition where both thesecomponents and other any component are mixed in use, depending on theapplication.

(Application)

A cured product of the curable composition of the present invention canbe used in, for example, a potting material or a sealing material. Acured product of the curable composition of the present invention can beused by, for example, filling any void (for example, a bonding sectionof a housing and a printed board, or a space between a metal terminalsection and a mold resin subjected to resin-molding) of an electronicmember with the cured product, and drying the resultant after suchfilling.

The temperature in a treatment (for example, filling and/or drying)using the curable composition of the present invention is not limited aslong as the temperature is in the range of 20° C. or more and less than200° C., and the temperature is preferably in the range of 50° C. ormore and less than 180° C.

The curing time of the curable composition of the present invention canbe appropriately selected as any time at which a crosslinking reactionand an adhesion reaction to the base material are completed, and can begenerally preferably 5 minutes to 24 hours, more preferably 10 minutesto 12 hours.

In order that a cured product (for example, a potting material or asealing material) having higher abrasion resistance is formed, an objectto be treated is preferably washed with acetone, hydrofluoroether or thelike and thereafter dried for removal of an oily content on the wall ofany void, before the treatment with the curable composition of thepresent invention. The object can be further subjected to apre-treatment with UV ozone, oxygen plasma or the like, in addition tothe washing, thereby allowing abrasion resistance of the cured productto be more enhanced.

A primer treatment can be, if necessary, applied onto, for example, thewall of any void before the treatment with the curable composition ofthe present invention, thereby enhancing adhesiveness of a cured productformed from the curable composition and more enhancing abrasionresistance. The primer treatment may be performed in the same conditionsas those of a primer treatment with a silane coupling agent, accordingto an ordinary method.

Herein, various primers can also be used in combination in the casewhere the cured product obtained from the curable composition of thepresent invention is allowed to adhere to various base materials.

In one embodiment, the curable composition of the present invention,when use, may be further diluted with a solvent and thus used, dependingon the application and the intended use. Any of the fluorine-basedsolvents exemplified above can be used as the solvent for use in thedilution. For example, the composition may be used, with being dissolvedin a solvent such as 1,3-bis(trifluoromethyl)benzene, Fluorinert(manufactured by 3M), perfluorobutyl methyl ether or perfluorobutylethyl ether so that a desired concentration is achieved. In particular,the solvent is preferably used in the application of thin film coating.

The curable composition of the present invention enables a cured producthaving favorable adhesiveness to a metal or a plastic base material tobe formed, and thus can be useful particularly as an adhesive to beapplied to peripherals of electrical and electronic components andperipherals of in-car members. The curable composition of the presentinvention has a favorable elastic modulus particularly even at a lowtemperature, and thus can be usefully used in, for example, anautomobile member (for example, a sealing material, specifically, agasket), particularly an automobile member usable in a cool region (forexample, −50° C. or less).

A cured product of the curable composition of the present invention isfavorable in chemical resistance, acid resistance and base resistance.Such a cured product of the curable composition of the present inventioncan also be used in a chemical plant or a member for semiconductormanufacturing equipment.

The glass transition temperature of a cured product of the curablecomposition of the present invention can be a relatively low value. Thereason for this is because the curable composition of the presentinvention includes the compound having the PFPE¹. The curablecomposition of the present invention can be used in any applicationwhere the composition is used at a relatively low temperature, forexample, an automobile member (for example, sealing material,specifically, gasket), particularly an automobile member usable in acool region (for example, −50° C. or less).

A cured product of the curable composition of the present invention canbe inhibited from being increased in elastic modulus at a lowtemperature. A cured product of the curable composition of the presentinvention can be inhibited from being increased in, for example, theratio of the elastic modulus at −50° C. to the elastic modulus at 0° C.The curable composition of the present invention can be used in anyapplication where rubber properties are demanded ever, at a relativelylow temperature, for example, a chemical plant, semiconductormanufacturing equipment or the like.

The temperature of 1% decomposition of a cured product of the curablecomposition of the present invention can be, for example, the sametemperature as the temperature of 0.1% decomposition of a cured productof a composition including a silane compound having(OCF₂CF(CF₃))_(m)OCF₂CF₂O(CF(CF₃)CF₂O)_(n) as a perfluoro(poly)ethergroup. Accordingly, the curable composition of the present invention canbe used at a relatively high temperature.

EXAMPLES

The present invention is more specifically described with reference tothe following Examples, but is not intended to be limited to suchExamples. The occurrence order of repeating units constitutingperfluoro(poly)ether is not limited in the present Examples.

Example 1

Preparation of Curable Composition

Compound (B) as a cross-linking agent and a xylene solution containing2% of a Pt complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane as acuring catalyst were weighed in a glass vessel for mixing in amounts of4 parts by weight and 0.4 parts by weight, respectively, based on 100parts by weight of perfluoropolyether compound (A), and stirred andmixed, to prepare a curable composition.

Perfluoropolyether Compound (A)

-   CH₂═CHCH₂OCH₂CF₂(OC₂F₄)_(e)—(OCF₃)_(f)—CF₂CH₂OCH₂CH═CH₂    wherein e=48, f=37, and e/f=1.3

Production of Test Piece

The curable composition prepared in Example 1 was poured into a moldformed by polytetrafluoroethylene (PTPE), and heated at 150° C. for 1hour and thus cured, to produce a test piece having a size of 5 mm×200mm and a thickness of 0.2 mm.

Comparative Example 1

A curable composition was prepared in the same manner as in Example 1except that perfluoropolyether compound (C) was used instead ofperfluoropolyether compound (A).

Perfluoropolyether Compound (C)

-   CH₂═CHCH₂OCH₂CF₂(OCF₂CF(CF₃))_(m)OCF₂CF₂O(CF(CF₃)CF₂O)_(n)—CF₂CH₂OCH₂CH═CH₂    wherein, m+n=54

The resulting curable composition was cured to form a test piece and thedynamic viscoelasticity was measured, in the same manner as in Example1.

Evaluation of Dynamic Viscoelasticity

The test pieces obtained Example 1 and Comparative Example 1 weresubjected to dynamic viscoelasticity measurement with a tension-typeviscoelasticity measuring system (DMA).

Specifically, liquid nitrogen was used for cooling and the measurementwas performed at a frequency of 10 Hz and at a temperature-increasingrate of 2° C./min in the measurement temperature range from −140 to 50°C. The .resulting storage elastic modulus was used to calculate theratio of the elastic modulus at −50° C. to the elastic modulus at 0° C.(Elastic modulus at −50° C./Elastic modulus at 0° C.). The resultingstorage elastic modulus plot was used to calculate the glass transitiontemperature (Tg), The results are shown in Table 1. In Table 1, the“elastic modulus ratio” means a ratio of the “Elastic modulus at −50°C./Elastic modulus at 0° C.”.

TABLE 1 ratio of the Tg° C. elastic modulus Example 1 −107 2.5Comparative Example 1 −69 4.9

Comparative Example 2

A curable composition was prepared in the same manner as in Example 1except that perfluoropolyether compound (D) was used instead ofperfluoropolyether compound (A).

Perfluoropolyether compound (D)

-   CH₂═CHCH₂OCH₂CF₂(OC₂F₄)_(e)—(OCF₂)_(f)—CF₂CH₂OCH₂CH═CH₂ wherein    e=40, f=58, and e/f=0.7

The resulting curable composition was cured to form a test piece in thesame manner as in Example 1.

The Tg of the test piece obtained thereof was −122° C.

Thermogravimetric/Differential Thermal Analysis

The temperature of 1% decomposition of each of the curable compositionsobtained in Example 1 and Comparative Examples 1 and 2 was measured witha thermogravimetric/differential thermal analyzer (TG/DTA).

Specifically, 10 mg of a cured product was weighed in an aluminum panand such measurement was performed with an aluminum oxide powder (Al₂O₃)as a reference in the measurement temperature range from 25 to 600° C.at a temperature-increasing rate of 10° C./min under an air atmosphere.The temperature at which the weight was decreased by 1% based on 10 mgof the cured product weighted was defined as the temperature of 1%decomposition. The results are shown in Table 2.

TABLE 2 Temperature of 1% decomposition (° C.) Example 1 298 ComparativeExample 1 313 Comparative Example 2 211

As shown in Table 1, the cured product of the curable compositionobtained in Example 1 had lower Tg, and the rubber property of the curedproduct was maintained even at a low temperature. It was found that thecured product of the curable composition obtained in Example 1 had lowerelastic modulus, and the composition was suitable for the use at a lowtemperature such as −50° C.

The cured product of the curable composition obtained in Example 1 had alinear PFPE structure and the e/f ratio was 1.0 or more. It was foundthat the cured product of the curable composition of Example 1 wassuitable for the use at lower temperature, and was additionally suitablefor the use at higher temperature, because as shown in Table 2, thetemperature of 1% decomposition in Example 1 was same as that of thecured product of the curable composition of Comparative Example 1. Thecurable composition of Comparative Example 1 has a branched structurewithstanding at a high temperature, but did not satisfy the e/f ratio of1.0 or more.

INDUSTRIAL APPLICABILITY

The curable composition of the present invention can be suitablyutilized for forming a fluorine-containing sealing material torembedding any void (for example, a void at a display edge) betweenelectronic members such as a display and a printed board in electronicequipment, and can be used as an adhesive to be applied to peripheralsof electrical and electronic components and peripherals of in-carmembers.

1. A curable composition comprising: (A) a compound which is a compoundhaving two or more alkenyl groups and a perfluoro(poly)ether group inone molecule, wherein the perfluoro(poly)ether group is a grouprepresented by formula:—(OC₆F₁₂)_(a)—(OC₅F₁₀)_(b)—(OC₄F₈)_(c)—(OC₃X¹⁰₆)_(d)—(OC₂F₄)_(e)—(OCF₂)_(f)— wherein a, b, c and d are eachindependently an integer of 0 or more and 30 or less, e and f are eachindependently an integer of 1 or more and 200 or less, the sum of a, b,c, d, e and f is at least 5 or more, the occurrence order of therespective repeating units in parentheses with the subscript a, b, c, d,e or f is not limited in the formula, a ratio of e to f is 1.0 or more,and each X¹⁰, at each occurrence, is independently a hydrogen atom, afluorine atom or a chlorine atom; (B) an organosilicon compound whichhas two or more hydrogen atoms each bonding to a silicon atom, in onemolecule; and (C) a catalyst.
 2. The curable composition according toclaim 1, wherein (A) the compound having two or more alkenyl groups anda perfluoro(poly)ether group in one molecule is a compound representedby formula (I):CH₂═CH—R^(k1)—PFPE¹—R^(k1)—CH═CH₂   (I)wherein: each R^(k1), at each occurrence, independently represents asingle bond or a divalent organic group; and each PFPE¹, at eachoccurrence, independently represents—(OC₆F₁₂)_(a)—(OC₅F₁₀)_(b)—(OC₄F₈)_(c)—(OC₃X¹⁰₆)_(d)—(OC₂F₄)_(e)—(OCF₂)_(f)— wherein a, b, c and d are eachindependently an integer of 0 or more and 30 or less, e and f are eachindependently an integer of 1 or more and 200 or less, the sum of a, b,c, d, e and f is at least 5 or more, the occurrence order of therespective repeating units in parentheses with the subscript a, b, c, d,e or f is not limited in the formula, a ratio of e to f is 1.0 or more,and each X¹⁰, at each occurrence, is independently a hydrogen atom, afluorine atom or a chlorine atom.
 3. The curable composition accordingto claim 1, wherein a hydrogen atom bonding to a silicon atom in (B) theorganosilicon compound which has two or more hydrogen atoms each bondingto a silicon atom, in one molecule, is comprised in the range from 0.5to 5.0 mol based on 1 mol of an alkenyl group in (A) the compound havingtwo or more alkenyl groups and a perfluoro(poly)ether group in onemolecule.
 4. The curable composition according to claim 1, wherein (B)the organosilicon compound which has two or more hydrogen atoms eachbonding to a silicon atom, in one molecule, has at least one selectedfrom the group consisting of one or more monovalent perfluoroalkylgroups, monovalent perfluorooxyalkyl groups, divalent perfluoroalkylenegroups and divalent perfluorooxyalkylene groups, in a molecularstructure.
 5. The curable composition according to claim 1, wherein thecatalyst is a transition metal catalyst.
 6. The curable compositionaccording to claim 1, wherein the catalyst comprises at least onecomprising platinum, rhodium, ruthenium, iridium and palladium.
 7. Thecurable composition according to claim 1, wherein the catalyst comprisesplatinum.
 8. The curable composition according to claim 1, comprising0.1 to 500 ppm by mass of the catalyst in terms of metal atom relativeto (A) the compound having two or more alkenyl groups and aperfluoro(poly)ether group in one molecule.
 9. The curable compositionaccording to claim 1, wherein a ratio of the sum of e and f to the sumof a, b, c, d, e and f is 0.80 or more in (A) the compound having two ormore alkenyl groups and a perfluoro(poly)ether group in one molecule.10. The curable composition according to claim 1, wherein X¹⁰ is afluorine atom.